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Title:
METHOD FOR LINKING TWO OR MORE METALS FOR PHOTO AND ELECTRONIC MATERIALS
Document Type and Number:
WIPO Patent Application WO/2012/058285
Kind Code:
A2
Abstract:
Embodiments of the invention are directed to bimetallic substituted triazole compounds and methods to prepare the compounds. The compounds include at least one 1,2,3 -triazole that is substituted by two metal ions in the 1 and 4 or 5 position of the triazole ring. An iClick reaction between a metal acetylide and a metal azide results in the bimetallic substituted triazole ring. Depending on the metal acetylide and a metal azide used monomeric bimetallic substituted triazole compounds, oligomeric bimetallic triazole compounds, or polymeric bimetallic triazole compounds are formed. Polymeric bimetallic triazole compounds can be linear, branched, ladder, two-dimensional network, or three-dimensional networks.

Inventors:
VEIGE ADAM STEVEN (US)
DEL CASTILLO TREVOR (US)
MURRAY LESLIE JUSTIN (US)
Application Number:
US2011/057851
Publication Date:
May 03, 2012
Filing Date:
October 26, 2011
Export Citation:
Click for automatic bibliography generation   Help
Assignee:
UNIV FLORIDA (US)
VEIGE ADAM STEVEN (US)
DEL CASTILLO TREVOR (US)
MURRAY LESLIE JUSTIN (US)
International Classes:
C07F1/12; C07F15/04; C07F19/00
Other References:
DEL CASTILLO, T. J. ET AL.: '1, 3-Dipolar Cycloaddition between a Metal-azide and a Metal-acetylide: an Inorganic Version of a Click Reaction.' DALTON TRANS. vol. 40, 04 July 2011, pages 8140 - 8144
FORTMAN, G. C. ET AL.: 'A Versatile Gold Synthos for Acetylene C-H Bond Activation.' DALTON TRANS. vol. 39, 04 October 2010, pages 10382 - 10390
PARTYKA, D. V. ET AL.: 'Carbon-Gold Bond Formation through [3+2] Cycloaddition Reactions of Gold(I) Azides and Terminal Alkynes.' ORGANOMETALLICS vol. 26, 2007, pages 183 - 186
PARTYKA, D. V. ET AL.: 'Copper-Catalyzed Huisgen [3+2] Cycloaddition of Gold(I) Alkynyls with Benzyl Azide. Syntheses, Structures, and Optical Properties.' ORGANOMETALLICS vol. 28, 2009, pages 6171 - 6182
Attorney, Agent or Firm:
EISENSCHENK, Frank, C. et al. (Lloyd & EisenschenkP.O. Box 14295, Gainesville FL, US)
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Claims:
CLAIMS

We claim:

1 . A bimetallic substituted triazole compound, comprising one or more 1 .2,3- triazole units where at least one of the triazole units is substituted by two metal ions in the 1 and 4 or 5 positions.

2. The compound of claim 1 , wherein the one or more triazole units substituted with two metal ions are further substituted independently with an organic substituent in the 4 or 5 positions.

3. The compound of claim 1 , wherein the metal ions are independently Au, Ni, Pd, Pt, Ru. Fe, Mn, Rh, Ir, Cr, Cu, W or any other group 3-16 metal.

4. The compound of claim 1 , wherein one or more cluster complexes comprise one or both of the metal ions of the bimetallic substituted triazole compound, wherein at least one of the plurality of metal ions in the cluster complex is substituted by at least one of the triazole units.

5. The compound of claim 1 , further comprising at least one ligand to at least one metal ion.

6. The compound of claim 5, wherein the ligands are independently any phosphorous based ligands, nitrogen based ligands, cyclopentadienyl derivative, carbon monoxide, nitrosyl, alky L aryl, or pincer-type ligand.

7. The compound of claim 1, comprising a plurality of triazole units wherein at least one metal is attached to two triazole units.

8. The compound of claim 7, wherein a multiplicity of triazole units are connected by a multiplicity of metal ions as a linear polymeric chain or a poly meric network.

9. The compound of claim 7, wherein the polymeric network comprises tetrahedral metal ions.

10. The compound of claim 9, wherein the polymeric network comprises octahedral metal ions.

1 1. The compound of claim 10, wherein the polymeric network is a two- dimensional network.

12. The compound of claim 10, wherein the polymeric network is a three- dimensional network.

13. A method for the preparation of the bimetallic substituted triazole compound of claim 1 , comprising:

providing at least one metal acetylide;

providing at least one metal azide; and

combining the metal acetylide and the metal azide; wherein the azide and acetylide undergo cycloaddition to form a triazole ring, wherein the metal of the metal azide is a substituent at the 1 position of the triazole ring and the metal of the metal acetylide is a substituent at the 4 or 5 position of the triazole ring.

14. The method of claim 13, wherein the metal azides independently comprise a metal and 1 to 6 azide groups.

15. The method of claim 13, wherein the metal acetylides independently comprise a metal and 1 to 6 acetylide groups.

16. The method of claim 13, wherein the acetylide groups are independently unsubstituted or substituted with an organic group.

17. The method of claim 13, wherein the cycloaddition reaction is catalyzed by a copper (I) salt.

Description:
DESCRIPTION

METHOD FOR LINKING TWO OR MORE METALS FOR PHOTO AND ELECTRONIC

MATERIALS

BACKGROUND OF INVENTION

A Click reaction is one that yields a product quantitatively or nearly so while being tolerant to a wide range of solvents, including water, and pH conditions and having a strong thermodynamic driving force. These characteristics are attractive when designing new approaches to building small molecules and materials. Reactions that have the characteristics of a Click reaction were originally pursued in the field of drug discovery, and the approach has led to an immense number of potential drug targets in a manner that is easier and less expensive than earlier synthetic approaches used for drug discovery.

Of the reactions that are classified as Click reactions, the most recognized and prolifically applied is the Huisgen 1 , 3-dipolar cycloaddition between an alkyne and an azide to yield 1 ,4-disubstituted 1 ,2,3-triazole, as shown in Scheme 1, below. This reaction is particularly accessible due to: the ease of synthesis of the alkyne and azide functional reactants in nearly quantitative yields; the tolerance of the reaction to a wide variety of solvents, including water; the regioselectivity of the reaction toward synthesis of 1 ,4- disubstituted triazoles; and the high tolerance of alkyne and azide functional groups to most other functional groups. A Huisgen 1, 3-dipolar cycloaddition represents the qualities of a Click reaction so well that it is often referred to simply as "the click reaction".

Scheme 1

Despite the great activity of Click Chemistry and, particularly, the Huisgen cycloaddition in organic chemistry, there are few applications of these reactions in inorganic or organometallic chemistry, an inorganic Click (iClick) reaction or extensions to materials synthesis. Huisgen cycloaddition has been applied to the functionalization metal clusters with organic moieties and to the synthesis of organic ligands to be employed with metal ions. The Huisgen 1 , 3-dipolar cycloaddition reaction has not been explored to link two or more metal ions. Organobimetal c compounds from this click reaction should be useful as bimetallic catalysts, polymers, and 2- or 3 -dimensional covalent metal organic networks, including those where a plurality of identical or different metals are isolated and at least two metals are separated by a 1,2,3-triazole ring.

BRIEF SUMMARY

Embodiments of the invention are directed to bimetallic substituted triazoie compounds comprising one or more 1 ,2,3-triazole units where at least one of the triazoie units is substituted by two metal ions in the 1 and 4 or 5 positions. The triazoie units can be further substituted with an organic substituent in the 4 or the 5 position that is not substituted by the metal ion. The metal ions can be Au, Ni, Pd, Pt, Ru, Fe, Mn, Rh, Ir, Cr, Cu, W or any other group 3-16 metal. The compound can include at least one ligand attached to at least one metal ion, where the ligand can be, for example, a phosphorous based ligands, nitrogen based ligands, cyclopentadienyl derivative, carbon monoxide, nitrosyl, alkyl, aryl, or pincer- type ligand that can be neutral or charged and monodentate or chelating. In some embodiments of the invention, a plurality of triazoie units is present with at least one metal attached to two triazoie units. In other embodiments of the invention a multiplicity of triazoie units are connected by a multiplicity of metal ions as a linear polymeric chain or a polymeric network.

Other embodiments of the invention are directed to a method for the preparation of the bimetallic substituted triazoie compounds where at least one metal acctylide and at least one metal azide are combined and undergo cycloaddition to form a triazoie ring. The metal azide can be a metal with 1 to 6 azide groups and the metal acctylide can be a metal with 1 to 6 acetylide groups that can be unsubstituted or substituted with an organic group.

BRIEF DESCRIPTION OF DRAWINGS

Figure 1 shows the molecular structure of homobimetallic triazoie complex 3 1)5 according to an embodiment of the invention as determined by single crystal X-ray diffraction experiments.

Figure 2 shows a Ή NMR spectrum of a mixture of 3i,s and 3 1>4 according to an embodiment of the invention in CDC1 3 .

Figure 3 shows a P { 11 } NMR spectrum of a mixture of 3i, s and 3i, 4 , according to an embodiment of the invention referenced to PPh 3 as an external standard. Figure 4 shows a 1 C { ' H} NMR spectrum of a mixture of 3 1)5 and 3 1)4 according to an embodiment of the invention.

Figure 5 shows a 31 Ρ{Ή} NMR spectrum of a mixture of 3i, s and 3 1(4 at -40 °C according to an embodiment of the invention.

Fi ure 6 shows a FT-IR spectrum of a mixture of 3 1;S and 3i, , according to an embodiment of the invention.

DETAILED DISCLOSURE

Embodiments of the invention are directed to a method, an iClick reaction, where 1 ,3- dipolar cycloaddition is employed to link two or more metal ions upon combining a metal- coordinated a/.ide complex and a metal-coordinated alkyne complex with the formation of a

1.4- bimetallic substituted triazole as shown in Scheme 2, below, for reaction between a metallic monoacetylide and a metallic monoa/.ide where M and M' represent metal centers that can be the same metal or different metals, L is independently any ligand, and R is hydrogen or any organic substituent. In other embodiments of the invention, the cycloaddition can result in a 1,5-bimetallic substituted triazole, as shown in Scheme 3, or a combination of 1 ,4- and 1 ,5-bimetallic substituted triazole. The selectivity towards 1 ,4- or

1.5- addition depends upon the metal ion or ions and other substituents on the acetylide. In embodiments of the invention, one or both of M and M\ the metal centers, are not a single metal ion, rather, M and/or M' is a cluster complex where a plurality of one metal ion or a plurality of two or more metal ions reside as a cluster. In these embodiments of the invention, one or more metal ions of the cluster are bonded to at least one azide or to at least one acetylide. Although other ligands need not be present, the cluster can have one or more ligands, such as. but not limited to, carbon monoxide, halides, isocyanides, alkenes, or hydrides, included to stabilize the cluster complex.

Embodiments of the invention are directed to bimetallic complexes, trimetallic complexes, one-dimensional metallopolymers and metallooligomers, two-dimensional metal- organic networks, and three-dimensional metal lonetworks formed from azide and acetylide reagents. Each of these products, according to embodiments of the invention, can vary by the number and identity of the combined metal ions, ligands, regioselectivity of the addition product, coordination geometries, oxidation states, and redox combinations that permit these organometallic species to be used in a variety of applications. Currently, methods for linking two metals ions are limited, and linking two or more metal ions in a controllable fashion is difficult. The iClick reaction has a strong thermodynamic driving force that effectively couples nearly any metal azide and any metal acetylide rapidly and displays a quantitative or nearly quantitative efficiency. The iClick reaction can be catalyzed. For example a catalytic amount of copper (I) salt can be added to the reaction mixture, or formed in the reaction mixture by the addition of a copper (II) salt and copper metal or other reducing agent.

Scheme 2

Scheme

Tor bimetallic triazoles, as illustrated in Schemes 2 and 3, the metal ions, M and M' are independently a metal from groups 3-12 or a main group metal from groups 13- 16. For example the metal ions can be Au, Ni, Pd, Pt. Ru, Fe, Mn, Rh, Ir, Cr, Cu, and/or W ions. Ligands can be neutral or charged and can be monodentate or chelating. Common ligands include but are not limited to: phosphorous based ligands; nitrogen based ligands, including pyridine, bipyridine, and terpyridine; cyclopentadienyl derivatives; carbon monoxide; nitrosyl; alkyl; aryl; and pincer-type ligands. In some embodiments of the invention, the ligand can include functional groups to permit their association or bonding to a surface, incorporation into a resin, or polymerization to materials with fixed bimetallic triazole units for use as heterogeneous catalysts.

In these bimetallic triazoles, the R group is H, Ci-C 30 alkyl, C 6 -C 2 2 aryl, C 7 -C 3 o alkylaryl, C 7 -C 30 arylalkyl, C2-C29 heteroaryl, C 3 -C 3 o alkylheteroaryl, C 3 -C 30 heteroarylalkyl, C2-C30 alkenyl, C 8 -C 30 alkenylaryl, C«-C;,o arylalkenyl, C4-C30 alkenylheteroaryl, or C4-C30 heteroarylalkenyl attached at any possible carbon of the R group to the triple bond of the reagent acetylide and the C-C double bond of the product triazole. Alkyl groups can be linear, branched, multiply branched, cyclic, polycyclic, or any combination thereof. Aryl groups can be phenyl, fused ring, for example a naphthyl group, or multi-ring, for example biphenyl groups, with any geometry or substitution pattern. Alkylaryl groups are those connected to the triple bond of the reagent acetylide at any carbon of an aryl ring which is substituted with one or more alkyl groups, where an alkyl portion can be an alkylene chain disposed between two aryl portions. Arylalkyl groups are those connected to the triple bond of the reagent at any carbon of the alkyl portion and have one or more aryl groups attached at any carbon of the alkyl portion or inserted within the alkyl portion of the group. I leteroaryl groups contain one or more five-membered or larger aromatic heterocyclic rings where one or more heteroatoms, for example, O, N, or S, are included in the aromatic ring and can be a single ring, fused rings, or multi-ring, where one or more ring of the fused or multi-ring group has one or more heteroatoms. Alkenyl groups can have one or more double bonds situated anywhere in the group where multiple double bonds can be isolated, conjugated, or a mixture of isolated and conjugated double bonds and where the alkenyl group can be a vinyl group or an internal double bond with any E or Z in geometry or any combination of vinyl with E or Z geometry for multiple double bonds. Any R groups can be substituted at any position with a hydroxy, C1-C30 alkoxy, C 6 -Ci4 aryloxy, C7-C30 arylalkyloxy, C 2 -C 3 o alkenyloxy, C 2 -C 3 o alkynyloxy, Cg-C 3 o arylalkenyloxy, C8-C30 arylalkynyloxy, C0 2 H, C 2 -C 30 alkylester, C7-C 15 arylester, C 8 - jo alkylarylester, C 3 -C 3 o alkenylester, C 3 -C 30 alkynylester, NH 2 , C1-Q30 alkylamino, C 6 -Ci 4 arylamino, C 7 -C 3 o (arylalkyl)amino, C 2 -C 3 o alkenylamino, C2-Q30 alkynylamino, Cs-C 3 o (arylalkenyl)amino, Cg-CNo (arylalkynyl)amino,C 2 -C 3 o dialkylamino, C12-C28 diarylamino, C 4 -C 3 o dialkenylamino, C 4 -C 3 o dialkynylamino, C7-C30 aryl(alkyl)amino, C7-C30 di(arylalkyl)amino, C 8 -C 3 o alkyl(arylalkyl)amino, C 15 -C 3 o aiy 1 ( ar y 1 a 1 ky 1 ) am i n , C 8 -C 3 o alkenyl(aryl)amino, C 8 -C 3 o alkynyl(aryl)amino C(0)NH 2 (amido), C 2 -C 30 alkylamido, C7-C 14 arylamido, C 8 -C 0 (arylalkyl)amido, C 2 -C 30 dialkylamido, C12-C28 diarylamido, C -C 3 o aryl(alkyl)amido, C15-C30 di(arylalkyl)amido, C9-C30 alkyl(arylalkyl)amido, Ci 6 -C 3 o aryl(arylalkyl)amido, thiol, Ci-C 30 hydroxyalkyl, C 6 -Ci4 hydroxyaryl, C7-C30 hydroxyarylalkyl, C 3 -C 3 o hydroxyalkenyl, C3-C30 hydroxyalkynyl, C 8 -C3 0 hydroxyarylalkenyl, C 8 -C3o hydroxyarylalkynyl, C3-C30 poly ether, C3-C30 polyetherester, C 3 - C30 polyester C3-C30 polyamino, C 3 -C 3 o polyaminoamido, C 3 -C 30 polyaminoether, C3-C30 polyaminoester, C3-C30 polyamidoester C3-C 3 oalkylsulfonic acid, C 3 -C 30 alkylsulfonate salt, C I -C J O carboxylate salt, thiocarboxylate salt, dithiocarboxylate salt or C 3 -C3oalkylCi-C 4 trialkyammonium salt. Asymmetric functional groups, such as ester and amido, can have either orientation with respect to their orientation relative to the triazole ring. Heteroatoms in substituents can be at any position of those substituents, for example, oxygen of an ether or ester or nitrogen of an amine or amide can be in the alpha, beta, gamma or any other position relative to the point of attachment to the base portion of the R group. Heteroatom containing substituents can have a plurality of heteroatoms, for example ether can be a monoether, a diether or a poly ether, amine can be a monoamine, a diamine or a polyamine. ester can be a monoester, a diester, or a polyester, and amide can be a monoamide, a diamidc or a polyamide. Ethers and esters groups can be thioethers, thioesters and hydroxy groups can be thiol (mercapto) groups, where sulfur is substituted for oxygen. Salts can be those of alkali or alkali earth metals, ammonium salts, or phosphonium salts.

In an embodiment of the invention, linear metallopolymers can be formed by the addition of // s-dia/.ide octahedral complexes with rr /is'-diacetylide octahedral complexes, as shown below in Scheme 4. Inclusion or substitution of other geometries, for example cis- diazide and c .v-diaeetylide octahedral complexes, or disubstituted tetrahedral complexes, allows for the preparation of cyclic or macrocyclic metallopolymers. These metallopolymers can display extended electron derealization through multiple metal centers linked by triazole rings. Such conjugated polymers can be used in applications that exploit their non-linear optical properties, such as optical signal processing, switching, and frequency generation in optical data storage, optical communication, and optical image generation devices. Variation in the triazole structure allows control of the effective π conjugation length in these polymers, which determines the polymer's optical gap. The structure of R is as for the bimetallic triazoles described above. As a plurality of metallic diacetylide and metallic diazide can be used, a plurality of different Ms and/or M's can be included in a single polymer. The metals can be any selected from group 3-12 metals and main group metals from groups 13-16. For example the metals can be Au, Ni, Pd, Pt, Ru, Fe, Mn, Rh. Ir, Cr, Cu, and/or W. A plurality of different R groups can be used where a single metallic diacetylide has two different R groups, an asymmetric metallic diacetylide, or when two or more different metallic diacetylides are used where the diacetylides are symmetric, asymmetric, or any combination thereof. Polymers with different degrees of polymerization can be formed by varying the ratio of the metallic diacetalide and metallic diazide reagents, for example, a ratio of n/n+1 or n+l/n to yield azide end-groups or acetalide end-groups, respectively. The linear metallopolymer, which can be considered a linear metallooligomer, is formed when n/n+1 is relatively small, for example when n/n+1 is about 9/9+1 or less.

In another embodiment of the invention, one or more metallic monoacetylides and/or metallic monoazides are included with the metallic diacetylides and metallic diazides to control the degree of polymerization of the metallopolymers. In one embodiment of the invention, when one or more metallic monoacetylides are employed, a portion of the R groups can have functionality appropriate for use of the metallopolymers or metal looligomers as macromers for a second polymerization. The functional R groups can be only on metallic monoacetylides or they can be included in a portion of the metallic diacetylides. For example a vinyl group, such as an acrylate. methacrylate, or styrene group can be included in the metallic monoacetylides, or a cyclic ether, for example an epoxide, can be included for an addition chain growth polymerization of the macromer, or its copolymerization with a second monomer with like or copolymerizable group for crosslinking the metallopolymer or inclusion of the metallopolymer, into a resin at a small quantity. In another embodiment of the invention, the R groups of a portion of the metallic monoacetylides can include functionality that allows the linear metallopolymers or linear metallooligomers to be used as a macromer by a condensation or addition step growth polymerization with a complementary monomer. Alternately an organic diacetylide and/or an organic diazide can be included into the iClick reaction mixture with the metallic diacetylides and metallic diazides to decouple the effective π conjugation length from the degree of polymerization of the polymer, where the proportion of metallic diacetylides and metallic diazides to all diacetylides and diazides defines the conjugation length while the proportions of all diazides to all diacetylides define the molecular weight of the linear polymer. By inclusion of metallic or organic tri-, terra-, penta-, or hexaacetylides and/or metallic or organic tri-, terra-, penta-, or hexatriazides into the mixture of diazides and diacetylides, networks can be formed.

In another embodiment of the invention the iClick reaction between: metal tetraazides and metal tetraacetylides; metal tetraazides and metal diacetylides; metal diazides and metal tetraacctylides; metal triazides and metal triacety ides; metal triazides and metal diacetylides; or metal diazides and metal triacetyiides results in the formation of a two-dimensional network when the R groups are small; for example, hydrogen or methyl as the acetyl ide and azides are coplanar with the metal ions. Ladder polymer can result in some embodiments of the invention where metal triacetylides and/or metal triazides arc included. Scheme 5, below, illustrates the formation of a two-dimensional network using reaction between square planar metal centers where ligands are omitted for clarity in the illustrated product.

Scheme 5

In some embodiments of the invention, 2-dimensional networks can be synthesized by reaction of mixtures of metal complexes that include CM-, trans-, and/or mer- acetylide or azido complexes, with or without included square planar metal complexes, where the 2- dimensional networks are of finite proportions and are effectively nanoparticle sized sheets or flakes rather than the extended sheets that can be considered larger "bulk " materials. Such nanoparticulate two-dimensional networks can be employed as heterogeneous catalysts, as- synthesized compound or after post-synthesis modification, such as after metal ion doping or controlled oxidation, or as photo-induced catalysts where the network is generated with hetero-metal centers with photochemistry tuned by the ligands, for example bipyridines or terpyridines, on the metal center. Use of fra/w-diacetylides or azides employed with square planar tetraacetylides or tetraazides in a complementary manner can result in "bulk" two- dimensional networks. These "bulk" two-dimensional networks share some features with metal organic frameworks (MOFs), such that they can be used as heterogeneous catalysts or as surfaces for gas storage. Thin films of the two-dimensional polymers can be grown or spin-coated after synthesis onto electrode surfaces for use as electrocatalysts for redox reactions due to simultaneous conductivity and catalytic activity. The two-dimensional iClick formed materials are advantageous over MOFs due to: the presence of strong covalcnt metal -carbon and metal-nitrogen bonds rather than the dative interactions of MOFs; surfaces where different metal ions residing in specific coordination environments rather than MOFs which inherently lack site specificity; mononuclear metal nodes having strict geometric constraints due to the geometry imposed by the reactant acetylide and a/ide complexes; and the order imposed by a 2-dimensional network from iClick reactions that occur at ambient temperatures rather than those for MOFs where synthesis is typically carried out under hydro thermal conditions at elevated temperatures.

In another embodiment of the invention, three-dimensional networks are formed where either homoleptic azides or acetylides, in octahedral or tetrahedral geometries, are paired with their complementary /ram-diacetylide or diazide, as shown in Schemes 6 and 7, below. Scheme 6 illustrates a network from a hexaacetylide and a diazide, where ligands are not shown in the network for easier view, that has a cubic cell. Scheme 7 shows only the reagent mixture, but does not show the diamond-like cell of the resulting network imposed by the tetrahedral geometry of one of the reagents. These materials have some similar properties as those for zeolitic imidazolate frameworks (ZIFs), which include high porosity and stability. Three-dimensional networks from iClick reactions are readily directed toward a specific utility through the choice of substituent on the acetylide ligand(s) and by modification of the two N-donor coordination sites that are available in the three-dimensional network. The three-dimensional networks can be constructed for use as gas storage/separation network, size-selective heterogeneous catalysts, or lithium ion battery separators.

Scheme 6

Scheme 7

METHODS AND MATERIALS

General Methods

Glassware was oven dried before use. Pentane, toluene, and diethyl ether (Et 2 0) were dried using a Glass Contours drying column. Benzene- g and chloroform-c/ / (Cambridge Isotopes) were dried over sodium-benzophenone ketyl and distilled or vacuum transferred and stored over 4A molecular sieves. Commercially available PPh 3 AuCl and TMSN 3 were used without further purification. Commercially available phenylacetylene was distilled before use. Ph 3 PAuCCPh and Ph 3 PAuN 3 and PPh 3 Au-C≡CPh were prepared according to literature procedures. NMR spectra were obtained on Varian Mercury Broad Band 300 MHz, Varian Mercury 300 MHz, or on Varian Inova 500 MHz spectrometers. Chemical shifts are

1 13 1

reported in δ (ppm). For H and C{ H} NMR spectra, the solvent resonance was referenced as an internal reference, and for ^P ^H} NMR spectrum, the 85% H 3 P0 4 resonance was referenced as an external standard. Elemental analyses were performed at Complete Analysis Laboratory Inc., Parsippany, New Jersey. FT-IR spectra were recorded on a Thermo scientific instrument.

Synthesis of a homo-bimetallic complex

As shown in Scheme 8, below, combining equal molar amounts of reagents 1 and 2 in benzene produces complex 3i,s (97%) and 3i, (<3%) in 88% yield within 24 hours. Single colorless crystals grow from a concentrated benzene solution of 3 1; s. Figure 1 shows the molecular structure of 31 ,5 as determined from a single crystal X-ray diffraction experiment. Tables 1 through 4, below, give crystal structure data for 3i )5 and Tables 5 and 6, below, give computationally determined geometries for 3i, s and 31,4. Additional support for the identification of complex 3i,j comes from NMR spectroscopy. Figure 2 is a Ή NMR spectrum of 1.5 and 3 li4 in CDC1 3 , Figure 3 is a j , P { ' H } NMR spectrum of 3i, s and 3i, 4 , and Figure 4 is a 1 { ! H} NMR spectrum of 3 li5 and 3 M . Two resonances appear in the 31 P NMR spectrum at 43.93 and 3 1 .45 ppm for the two distinct phosphorous nuclei on complex 31,5. Cooling the solution to -40 °C reveals two addition P resonances attributable to 3 1(4 (Figure 5). Figure 6 is an IR spectrum of 3i )5 and 3 ) <4 mixture.

Scheme 8

p h ^_ Au pp h3 88% Ph^N Ph 3 PAu^ N'

2 3i 5 3i,4

97% <3%

Synthesis Details

A scalable NMR tube was charged with Ph 3 PAuCCPh (10 mg, 0.018 mmol), Pf PAuNi (9 mg, 0.01 8 mmol), and benzene-i¾ (0.6 mL). After 24 hours clear colorless crystals deposit along the sides of the NMR tube. Crystals were collected and washed with pentane to give the major product 31,5 and < 3% minor product 3 1)4 (17 mg, 89 % yield). 3 ( i j5) : Ή NMR (300 MHz, CDCI3), δ (ppm): 8.43 (d, J = 9 Hz), 7.1 -7.6 (m, aromatic). Ρ{Ή} NMR ( 121 .16 MHz, CDCI3, 25 °C), δ (ppm): 43.93 (bs, PAuC), 31 .45 (bs. PAuN). 13 C{ 'H} NMR (75 MHz, CDCI3), δ (ppm): 136.6 (s, Caromatic, triazolate). 134.2 (d, J PC = 14 Hz, o-C, overlapping, C-Au-P(C 6 H 5 ) 3 and N-Au-P(C 6 H 5 ) 3 , 131.5 (bs, i-C, overlapping, C-Au-P(C 6 H 5 ) 3 and N-Au-P(C 6 H 5 ) 3 , 129.1 (d, J PC = 1 1 Hz, m-C and p-C, overlapping, C-Au-P(C 6 H 5 ) 3 and N- Au-P(C 6 H 5 ) 3 , 127.9 (s, C ar omatic, triazolate), 126.4 (s, C arom atic, triazolate), 125.4 (s, Caromatic, triazolate). 3 ( i ,4) : l NMR (300 MHz, CDCI3), δ (ppm): 8.6 (d, J = 9 Hz), aromatic resoances overlapping with 3 ( i ;5) between 7.1-7.6. 31 P{ l H} NMR (121.16 MHz, CDC1 3 , -40 °C), δ (ppm): 43.93 (s, PAuC), 31.45 (s, PAuN). Anal. Calcd. for C 44 H 5 N 3 P 2 Au 2 : C, 49.78; H, 3.32; N, 3.96. Found: C, 49.86; H, 3.41 ; N, 3.88. Table 1. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (A 2 x 10 3 ) for 3i.s. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

Atom X y z U(eq)

Aul 8914(1) 5890(1) 3253(1) 19(1)

Au2 8468(1) 5595(1) 4198(1) 21(1)

PI 8059(1) 6682(1) 2920(1) 19(1)

P2 7329(1) 6217(1) 4476(1) 27(1)

Nl 9633(2) 5158(2) 3574(1) 20(1)

N2 10267(2) 4683(2) 3452(1) 28(1)

N3 10514(2) 4236(2) 3737(1) 28(1)

CI 9453(3) 5018(2) 3941(1) 18(1)

C2 10022(3) 4430(3) 4039(1) 21(1)

C3 10111(3) 4014(3) 4390(1) 25(1)

C4 9562(7) 4050(8) 4675(3) 29(3)

C5 9657(7) 3636(8) 5001(3) 34(3)

C6 10293(7) 3069(8) 5028(4) 25(3)

C7 10815(9) 2945(7) 4711(4) 30(4)

C8 10753(10) 3388(9) 4404(4) 33(4)

C4 1 9782(6) 4390(7) 4735(3) 25(3)

C5 1 9847(6) 4009(8) 5075(3) 32(3)

C6 1 10228(7) 3316(8) 5104(4) 30(3)

C7 1 10589(9) 2975(7) 4803(4) 31(3)

C8 1 10536(9) 3355(8) 4438(4) 29(4)

C9 7056(3) 5810(3) 4930(1) 27(1)

CIO 6202(3) 5729(3) 5055(2) 44(2)

Cll 6043(4) 5396(4) 5400(2) 55(2) '

C12 6722(4) 5145(4) 5621(2) 51(2)

C13 7564(3) 5234(3) 5505(2) 38(1)

C14 7729(3) 5565(3) 5157(1) 31(1)

C15 7538(3) 7231(2) 4558(1) 38(1)

C16 7101(8) 7607(3) 4845(2) 49(3)

C17 7308(12) 8371(3) 4935(2) 61(4)

C18 7952(10) 8760(3) 4738(2) 51(4)

C19 8388(6) 8385(4) 4451(4) 62(5)

C20 8181(5) 7620(4) 4361(3) 41(5)

C16' 7358(18) 7658(9) 4912(6) 49(6)

C17' 7669(19) 8424(9) 4966(4) 46(6)

C18' 8250(20) 8724(10) 4711(5) 60(6)

C19* 8434(12) 8337(10) 4380(6) 51(8)

C20' 8057(16) 7605(9) 4319(5) 42(8)

C21 6341(3) 6148(3) 4206(2) 34(1)

C22 5706(4) 6716(4) 4190(2) 61(2)

C23 4951(4) 6592(5) 3991(2) 75(2)

C24 4816(3) 5920(4) 3801(2) 57(2)

C25 5428(3) 5343(4) 3812(2) 48(2)

C26 6184(3) 5459(3) 4014(2) 42(1) Table 1 cont.

Atom X y z U(eq)

C27 7690(3) 7506(3) 3190( 1 ) 21(1)

C28 6876(7) 7739(8) 3238(4) 35(3)

C29 6655(7) 8402(8) 3454(4) 31(3)

C30 7316(8) 8862(7) 3584(3) 21(3)

C31 8153(9) 8664(7) 3518(3) 27(3)

C32 8363(8) 8009(7) 3328(4) 26(3)

C28' 6852(6) 7477(8) 3359(4) 23(3)

C29 * 6579(8) 8106(9) 3569(4) 34(4)

C30' 7072( 10) 8729(9) 3619(4) 37(4)

C31 * 7899(12) 8748(10) 3464(5) 46(5)

C32' 8195(10) 81 15(9) 3251(5) 36(4)

C33 8582(3) 7108(3) 2517(1 ) 19(1)

C34 8365(3) 7843(3) 2378( 1 ) 24(1)

C35 8780(3) 8130(3) 2065( 1 ) 29(1)

C36 9408(3) 7694(3) 1890(1) 33(1)

C37 9624(3) 6971(3) 2023(1) 31(1)

C38 9219(3) 6676(3) 2338(1) 25(1)

C39 7120(3) 6174(3) 2733(1) 20(1)

C40 6770(3) 6362(3) 2393( 1 ) 23( 1 )

C41 6122(3) 5905(3) 2238(1) 30(1)

C42 5813(3) 5265(3) 2423(1) 29(1)

C43 6139(3) 5086(3) 2771(2) 38(1)

C44 6798(3) 5532(3) 2924(2) 36(1)

C45 4057(4) 3795(4) 2519(2) 57(2)

C46 3524(4) 4396(4) 2590(2) 58(2)

C47 3201(4) 4522(3) 2931(2) 59(2)

C48 3421(4) 4032(4) 3221(2) 66(2)

C49 3987(4) 3406(4) 3150(2) 58(2)

C50 4295(3) 3310(4) 2801(2) 52(2)

C51 7654(5) 7447(4) 1222(3) 44(4)

C52 7543(5) 6747(5) 1410(2) 36(3)

C53 6862(7) 6255(4) 1315(2) 42(3)

C54 6291(6) 6464(5) 1032(2) 40(4)

C55 6402(5) 7165(6) 844(2) 45(3)

C56 7083(5) 7656(4) 939(3) 37(5)

C51 1 7545(5) 7313(6) 1200(3) 51(5)

C52' 7268(6) 6586(6) 1321(3) 57(4)

C53' 6457(7) 6308(4) 1217(3) 40(3)

C54 1 5924(6) 6758(5) 991(2) 34(3)

C55 1 6201(5) 7485(5) 869(2) 40(3)

C56 1 7012(6) 7762(4) 974(3) 64(7) Table 2. Bond lengths (in A) for 3 i, s .

Bond Length Bond Length Bond Length

Aul-N l 2.032(3) C39-C44 1.392(6) C51'-C52' 1.39( 1 )

Aul -Pl 2.2416(12) C40-C41 1.385(6) C51 '-C56' 1 .39( 1 )

Au2-Cl 2.035(4) C41 -C42 1.370(6) C52'-C53' 1 .39( 1 )

Au2-P2 2.2846(12) C7'-C8' 1.465(19) C53'-C54' 1.39(1)

P1-C27 1.807(5) C9-C14 1.386(7) C54'-C55' 1.39(1 )

P1 -C33 1.808(4) C9-C10 1.399(7) C55'-C56' 1.39(1)

P1 -C39 1.819(4) C l O-C l l 1.384(8)

P2 -C I 5 1.796(4) C11-C12 1.381(8)

P2 -C21 1.810(5) C12-C13 1.373(7)

P2 -C9 1.820(5) C13-C14 1.394(7)

N3-N2 1.332(5) C 15-C20 * 1.337(18)

N3-C2 1.365(5) C15-C16 1.39(1)

N1-N2 1.346(5) C15-C20 1.39(1)

Nl-Cl 1.368(5) C15-C16' 1.49(2)

C1 -C2 1.383(6) C16-C17 1.39(1)

C2-C3 1.457(6) C17-C18 1.39(1)

C3-C8' 1.319(14) C18-C19 1.39(1)

C3-C4 1.327(11) C19-C20 1.39(1)

C3-C8 1.463(16) C16'-C17' 1.415(14)

C3-C4' 1.486(11) C 17'-C 1 ' 1.376(14)

C4-C5 1.377(14) C18'-C19' 1.393(15)

C5-C6 1.385(16) C19'-C20' 1.402(14)

C6-C7 1.410(17) C21-C22 1.384(6)

C7-C8 1.34(2) C21-C26 1.390(7)

C4'-C5' 1.387(13) C22-C23 1.382(7)

C5'-C6' 1.330(15) C23-C24 1.357(8)

C6'-C7' 1.349(17) C24-C25 1.370(7)

C27-C28' 1.429(12) C25-C26 1.387(7)

C27-C32 1.439(13) C27-C32' 1.323(15)

C28-C29 1.419(14) C27-C28 1.329(1 1)

C29-C30 1.372(16) C42-C43 1.381(7)

C30-C31 1.356(17) C43-C44 1.386(6)

C31-C32 1.354(16) C45-C46 1.345(8)

C28'-C29' 1.385(15) C45-C50 1.362(9)

C29'-C30' 1.324(18) C46-C47 1.339(9)

C30'-C31' 1.39(2) C47-C48 1.380(9)

C31'-C32' 1.41(2) C48-C49 1.409(9)

C33-C38 1.388(6) C49-C50 1.350(8)

C33-C34 1.400(6) C51-C52 1.39(1)

C34-C35 1.383(6) C51-C56 1.39(1)

C35-C36 1.375(7) C52-C53 1.39(1)

C36-C37 1.373(7) C53-C54 1.39(1)

C37-C38 1.387(6) C54-C55 1.39(1)

C39-C40 1.373(6) C55-C56 1.39(1) Table 3. Bond angles (°) for 3i, s .

Bond Angle Bond Angle Bond Angle

Nl-Aul-Pl 176.9(1) C4-C3-C2 125.6(6) C22-C21-C26 117.3(5)

Cl-Au2-P2 177.99(12) C8'-C3-C8 13.7(9) C22-C21-P2 124.8(5)

C27-P1-C33 104.6(2) C4-C3-C8 116.1(9) C26-C21-P2 117.9(4)

C27-P1-C39 108.80(19) C2-C3-C8 117.0(7) C23-C22-C21 120.5(6)

C33-P1-C39 104.8(2) C8'-C3-C4' 115.8(8) C24-C23-C22 121.3(6)

C27-Pl-Aul 111.98(15) C4-C3-C4' 28.5(5) C23-C24-C25 119.7(6)

C33-Pl-Aul 114.18(14) C2-C3-C4' 118.4(5) C24-C25-C26 119.4(6)

C39-Pl-Aul 111.97(15) C8-C3-C4' 121.5(8) C25-C26-C21 121.8(5)

C15-P2 -C21 107.6(2) C3-C4-C5 124.1(9) C32'-C27-C28 107.2(9)

C15-P2 -C9 105.5(2) C4-C5-C6 119.9(11) C32'-C27-C28' 119.3(9)

C21-P2 -C9 105.0(2) C5-C6-C7 116.9(11) C39-C40-C41 120.4(4)

C15-P2 -Au2 112.77(16) C8-C7-C6 122.4(13) C42-C41-C40 120.8(5)

C21-P2 -Au2 112.54(18) C7-C8-C3 119.5(13) C41-C42-C43 119.3(4)

C9-P2 -Au2 112.88(15) C5'-C4'-C3 120.1(9) C42-C43-C44 120.2(5)

N2-N3-C2 107.9(4) C6'-C5'-C4' 121.5(11) C43-C44-C39 120.2(5)

N2-N1-C1 110.7(3) C5'-C6'-C7' 120.6(12) C46-C45-C50 119.5(7)

N2-Nl-Aul 126.0(3) C6'-C7'-C8' 120.0(12) C47-C46-C45 121.7(7)

Cl-Nl-Aul 122.8(3) C3-C8'-C7' 121.6(12) C46-C47-C48 119.9(6)

N3-N2-N1 108.0(4) C14-C9-C10 119.1(5) C47-C48-C49 118.8(6)

N1-C1-C2 104.1(4) C14-C9-P2 117.9(4) C50-C49-C48 118.7(6)

Nl-Cl-Au2 120.2(3) C10-C9-P2 123.0(4) C49-C50-C45 121.4(6)

C2-Cl-Au2 135.6(3) C11-C10-C9 119.7(5) C52-C51-C56 120.0(8)

N3-C2-C1 109.3(4) C12-C11-C10 120.5(5) C27-C32'-C31' ! 20.8(13)

N3-C2-C3 121.0(4) C13-C12-C11 120.5(6) C38-C33-C34 119.2(4)

C1-C2-C3 129.6(4) C12-C13-C14 119.4(5) C38-C33-P1 117.9(3)

C8'-C3-C4 105.0(8) C9-C14-C13 120.8(5) C34-C33-P1 122.9(3)

C8'-C3-C2 125.4(7) C20'-C15-C16 122.9(8) C35-C34-C33 120.0(4)

C20'-C15-C20 10.0(12) C28-C27-C28' 25.9(6) C36-C35-C34 120.2(5)

C16-C15-C20 120.0(6) C32'-C27-C32 16.8(8) C37-C36-C35 120.4(5)

C20'-C15-C16' 114.9(11) C28-C27-C32 117.0(8) C36-C37-C38 120.3(5)

C16-C15-C16' 18.4(9) C28'-C27-C32 121.8(7) C37-C38-C33 120.0(4)

C20-C15-C16' 109.2(7) C32'-C27-P1 121.6(7) C40-C39-C44 119.0(4)

C20'-C15-P2 117.9(8) C28-C27-P1 127.1(6) C40-C39-P1 121.9(3)

C16-C15-P2 119.0(4) C28'-C27-P1 119.1(6) C44-C39-P1 118.8(4)

C20-C15-P2 120.7(4) C32-C27-P1 115.4(6) C53-C52-C51 120.0(7)

C16'-C15-P2 125.7(7) C27-C28-C29 122.7(9) C52-C53-C54 120.0(8)

C15-C16-C17 120.(7) C30-C29-C28 118.0(9) C53-C54-C55 120.0(8)

C18-C17-C16 120.0(9) C31-C30-C29 120.1(10) C54-C55-C56 120.0(8)

C19-C18-C17 120.0(9) C32-C31-C30 121.7(11) C55-C56-C51 120.1(8)

C18-C19-C20 120.0(9) C31-C32-C27 120(1) C52'-C51'-C56' 120.0(6)

C19-C20-C15 120.0(8) C29'-C28'-C27 118.7(10) C51'-C52'-C53' 120.0(6)

C17'-C16'-C15 120.8(13) C30'-C29 , -C28 l 122.0(12) C54'-C53'-C52' 120.0(6)

C18'-C17'-C16' 118.5(13) C29'-C30'-C31' 119.4(14) C55'-C54'-C53' 120.0(6)

C17'-C18'-C19' 121.5(14) C30'-C31'-C32' 119.7(14) C56'-C55'-C54' 120.0(6)

C18'-C19'-C20' 118.4(15) C15-C20'-C19' 125.4(15) C55'-C56'-C51' 120.0(6) Table 4. Anisotropic displacement parameters (A 2 x 10 3 ) for 3 (1 , 5) The anisotropic displacement factor exponent takes the form: -2π 2 [ h 2 a* 2 U n + . .+ 2 h k a* b* U 12

1 11 U22 U33 U23 U13 U12

Aul 19(1) 22(1) 17(1) 0(1) -1(1) 2(1)

Au2 22(1) 21(1) 19(1) -1(1) 2(1) 5(1)

PI 19(1) 20(1) 19(1) 0(1) 0(1) 1(1)

P2 32(1) 27(1) 24(1) 2(1) 6(1) 12(1)

Nl 22(2) 21(2) 18(2) 1(2) 0(2) 4(2)

N2 29(2) 36(3) 19(2) -4(2) 4(2) 8(2)

N3 25(2) 31 (3) 29(3) 0(2) 0(2) 4(2)

CI 17(2) 20(3) 16(2) -4(2) -2(2) -2(2)

C2 17(2) 26(3) 20(3) -3(2) 1(2) -3(2)

C3 17(2) 27(3) 31(3) 4(2) -2(2) 2(2)

C9 34(3) 24(3) 22(3) -4(2) 1 1(2) 5(2)

CIO 41(3) 62(4) 28(3) 3(3) 7(2) 10(3)

Cl l 43(4) 85(5) 35(4) 7(3) 16(3) -2(3)

C12 64(4) 64(4) 25(3) 9(3) 4(3) -13(3)

C13 47(3) 42(3) 25(3) 3(3) 2(2) -4(3)

C14 34(3) 31(3) 27(3) -1(2) 1(2) -1(2)

C15 40(3) 30(3) 43(4) -2(3) 0(3) 16(2)

C21 32(3) 45(3) 25(3) 9(3) 4(2) 13(2)

C22 60(4) 68(5) 56(5) -14(4) -11(3) 38(3)

C23 58(5) 100(6) 66(5) -2(5) -21(4) 43(4)

C24 29(3) 11 1(6) 32(4) 17(4) -2(3) 8(4)

C25 32(3) 66(4) 47(4) 1(3) 3(3) 0(3)

C26 26(3) 54(4) 46(4) 0(3) -1(3) 10(3)

C27 22(2) 24(3) 17(3) 3(2) -1(2) 3(2)

C33 19(2) 23(3) 15(2) -3(2) -4(2) -4(2)

C34 24(3) 25(3) 23(3) 0(2) 0(2) 1(2)

C35 32(3) 29(3) 25(3) 4(2) -2(2) -5(2)

C36 27(3) 42(3) 30(3) 5(3) 2(2) -1 1 (2)

C37 24(3) 36(3) 34(3) -4(3) 3(2) -1(2)

C38 20(2) 26(3) 28(3) 2(2) -6(2) -5(2)

C39 20(2) 17(2) 23(3) -2(2) 1(2) 2(2)

C40 20(2) 29(3) 20(3) 5(2) 0(2) -3(2)

C41 23(2) 41 (3) 26(3) 0(3) -3(2) -1 (2)

C42 22(3) 33(3) 32(3) -3(3) -6(2) -6(2)

C43 37(3) 41(3) 36(3) 10(3) -5(3) -18(3)

C44 39(3) 43(3) 26(3) 10(3) -8(2) -14(3)

C45 56(4) 47(4) 68(5) -2(4) 14(3) -14(3)

C46 55(4) 41(4) 78(6) 15(4) 2(4) -7(3)

C47 45(4) 33(4) 98(6) -4(4) 15(4) 9(3)

C48 71 (5) 68(5) 58(5) -13(4) 20(4) -10(4)

C49 59(4) 48(4) 65(5) 16(4) -17(4) 5(3)

C50 31(3) 45(4) 80(6) -17(4) 6(3) 5(3) Computational Results for 3j,s.

Table 5. Optimized Cartesian coordinates of ground-state (singlet) for 3| 5 .

Atom X y z

Au 3.13414 -0.50824 -0.12262

Au -3.1 182 -0.53687 0.00241

P 5.42199 -0.15626 0.03395

P -5.4768 -0.14276 0.01235

N -0.61742 -2.20306 -0.14505

N 1.09665 -0.87802 -0.21797

N 0.69437 -2.17095 -0.22824

C 0.00288 -0.06645 -0.10413

C -1.10297 -0.92136 -0.05757

C 0.09247 1.39864 -0.06948

C 0.95307 2.10346 -0.93354

C 1.03565 3.49634 -0.88894

C 0.25346 4.22122 0.0136

C -0.61287 3.53672 0.87043

C -0.68992 2.14434 0.83298

C -5.91906 1.64342 0.01789

C -7.04495 2.15246 0.68227

C -7.331 19 3.51873 0.63698

C -6.49876 4.38745 -0.07097 c -5.37225 3.88908 -0.7297

C -5.07873 2.52632 -0.68116

C -6.32574 -0.84244 -1.46235

C -7.46026 -0.25348 -2.04098

C -8.06834 -0.84089 -3.15225

C -7.55017 -2.01851 -3.69487

C -6.41668 -2.60632 -3.12886

C -5.80222 -2.01972 -2.0222

C -6.35486 -0.86439 1.4596 c -7.67905 -1.3248 1.39691

C -8.29609 -1.85073 2.53359

C -7.59838 -1.92331 3.74087

C -6.27752 -1.4749 3.80933

C -5.65567 -0.95371 2.67445

C 5.88167 1.61643 -0.09362

C 7.1 1208 2.03318 -0.62514

C 7.42779 3.39183 -0.68134

C 6.52032 4.34304 -0.2105

C 5.29125 3.93521 0.31247 c 4.96893 2.57899 0.36766

C 6.11015 -0.74971 1.62962

C 7.18882 -0.1 1658 2.26506

C 7.69091 -0.62316 3.46548

C 7.12198 -1.76176 4.03903 Table 5 cont

Atom X y z

C 6.04354 -2.39273 3.41448

C 5.53429 -1.88791 2.2182

C 6.37937 -1.01757 -1 .2754

C 7.66141 -1.54001 -1 .04726 c 8.35813 -2.1665 -2.08254

C 7.78291 -2.27718 -3.34966 c 6.50422 -1.76513 -3.58159 c 5.80208 -1 .1431 -2.54968

H 1 .53634 1 .55049 -1 .6648

H 1.70148 4.01637 -1 .57409

H 0.31409 5.30632 0.04552

H -1.22478 4.08839 1.58033

H -1.34892 1.61425 1.51396

H -7.69305 1.48654 1.24408

H -8.2039 3.90273 1.15863

H -6.72217 5.45055 -0.10224

H -4.71282 4.56127 -1 .2716

H -4.18823 2.14547 -1 .17465

H -7.86233 0.66931 -1.63301

H -8.9442 -0.37462 -3.5957

H -8.02297 -2.47179 -4.56206

H -6.00094 -3.5152 -3.55474

H -4.90622 -2.4667 -1.5988

H -8.22515 -1.28579 0.45903

H -9.32047 -2.20857 2.47283

H -8.07917 -2.33751 4.62306

H -5.72478 -1.54246 4.74225

H -4.61968 -0.62825 2.72318

H 7.81799 1.30128 -1.00644

H 8.38083 3.70563 - 1 .09838

H 6.76683 5.40019 -0.25973

H 4.57413 4.67014 0.66661

H 4.00144 2.2693 0.75343

H 7.62925 0.77659 1.83217

H 8.52326 -0.12343 3.95347

H 7.51 192 -2.15151 4.97534

H 5.58885 -3.27151 3.86266

H 4.68199 -2.37033 1.74639

H 8.1 1 183 -1.47102 -0.06167

H 9.3483 -2.57272 -1.89495

H 8.3252 -2.76995 -4.15194

H 6.04589 - 1.86095 -4.56174

H 4.79843 -0.76625 -2.72856 Computational Results for 3 1 ,4.

Table 6. Optimized Cartesian coordinates of ground-state ( singlet) for 31,4.

Atom X y z

Au -1.82905 1 .43078 -0.00219

Au 1.80779 0.57941 -0.01463

P -3.64515 -0.01271 -0.02323

P 2.67095 -1.64619 0.03194

N 0.66983 4.71031 0.03241

N -0.25841 2.76217 0.00994

N -0.488 4.10199 0.04587

C 1 .08321 2.50081 -0.03233

C 1.66763 3.77544 -0.02028

C 3.07652 4.19284 -0.041

C 4.1148 3.32287 -0.42138

C 5.44403 3.74601 -0.42721

C 5.77158 5.0539 -0.06228

C 4.74874 5.93288 0.30498 c 3.421 13 5.51019 0.31626

C 4.50421 -1.69995 0.15092

C 5.27954 -2.69228 -0.46774

C 6.66901 -2.68684 -0.3285

C 7.2948 -1.69385 0.42761

C 6.52977 -0.69946 1.04164

C 5.14198 -0.69716 0.90056

C 2.06152 -2.65286 1.44506

C 2.82407 -3.67318 2.03472

C 2.30272 -4.41835 3.094 c 1.01878 -4.15238 3.5745

C 0.25681 -3.13279 2.99973

C 0.77702 -2.38223 1.9448

C 2.25686 -2.62159 -1.47466

C 1.99567 -3.9997 -1.44581

C 1.6991 -4.68572 -2.62579

C 1.6622 -4.00425 -3.84419

C 1.9143 -2.62984 -3.88052

C 2.2033 -1.94001 -2.70249 c -3.76769 -1.04331 1.49495 c -4.24013 -2.36394 1.47533 c -4.337 -3.09353 2.6624 c -3.96546 -2.51205 3.87628

C -3.48846 -1.19838 3.90239

C -3.38389 -0.46813 2.71818

C -5.24227 0.88438 -0.13682

C -6.42828 0.37446 0.41409

C -7.62381 1.08287 0.28255

C -7.64473 2.30342 -0.39564

C -6.46652 2.82029 -0.93858 Table 6 cont.

Atom X y z

C -5.26797 2.1185 -0.80713

C -3.61676 -1.19425 -1 .42861

C -4.78912 -1.68816 -2.021

C -4.71137 -2.60508 -3.0709

C -3.46716 -3.0346 -3.53713

C -2.29585 -2.54062 -2.95837 c -2.36889 -1.6201 -1.91269

H 3.86991 2.3092 -0.72856

H 6.22563 3.05225 -0.73031

H 6.80712 5.38534 -0.07066

H 4.98703 6.95614 0.58689

H 2.62465 6.1905 0.59912

H 4.80264 -3.46168 -1.06769

H 7.26132 -3.45699 -0.8153

H 8.37651 -1.68941 0.53057

H 7.01 138 0.084 1.61971

H 4.55335 0.09176 1.3618

H 3.82895 -3.87839 1 .67751

H 2.90348 -5.20264 3.54667

H 0.61775 -4.73163 4.40193

H -0.73775 -2.91075 3.37638

H 0.19166 -1.5723 1.51737

H 2.01448 -4.53749 -0.50279

H 1.4974 -5.753 -2.59102

H 1.43574 -4.54077 -4.76178

H 1.88034 -2.0919 -4.82386

H 2.37954 -0.86767 -2.73202

H -4.52351 -2.82748 0.53526

H -4.70171 -4.11675 2.6361 1

H -4.04383 -3.08086 4.79886

H -3.19151 -0.74233 4.84261

H -2.99761 0.54778 2.74079

H -6.41783 -0.56579 0.95766

H -8.53651 0.68327 0.71609

H -8.57547 2.85579 -0.49148

H -6.47411 3.7767 -1.4533

H -4.34885 2.53606 -1.20994

H -5.76069 -1.34895 -1.67444

H -5.62411 -2.97785 -3.52768

H -3.41093 -3.745 -4.3575

H -1.3241 1 -2.8597 -3.32432

H -1.45576 -1.21808 -1.48139 It should be understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application.