Replacement Sheets of the Claims:

CLA S

What is claimed is:

1. A nanoparticle complex for the reduction of an organic compound comprising a nitro group to form an organic compound comprising an amine group, comprising:

a) one or more transition metal salts, or a combination of the transition metal salts; b) an iron salt; and

c) a residual element of a reducing agent;

wherein the nanoparticle complex is obtained by:

i) a reaction of the reducing agent with the one or more transition metal salts; ii) a reaction of the reducing agent with the one or more transition metal salts and the iron salt;

iii) a reaction of the reducing agent with a combination of the transition metal salts; or

iv) a reaction of the reducing agent with a combination of the transition metal salts and the iron salt; and

wherein the nanoparticle complex is formed in the absence of a ligand.

2. The composition of Claim 1, wherein the one or more transition metal salts, or a combination of the transition metal salts is selected from the group consisting of Fe-ppm Pd (Fe-Pd NPs), Fe-ppm Ni (Fe-Ni NPs) and Fe-ppm Pd + Ni NPs (Fe-Pd-Ni NPs).

3. The composition of Claim 1 or 2, further comprising a reaction medium selected from a group consisting of one or more surfactants and water, optionally further comprising a second organic solvent or mixtures of solvent, as a co-solvent.

4. The composition of any one of Claims 1 to 3, wherein the organic compound is selected from the group consisting of an aliphatic, aromatic, heteroaromatic or heterocyclic compound.

5. The composition of any one of Claims 1 to 4, wherein the transition metal salt is a nickel salt, copper salt or a palladium salt, or combinations thereof.

6. The composition of Claim 5, wherein the nickel salt is selected from the group consisting of NiCl₂, NiCl₂^»6H₂0, NiCl₂^«xH₂0, Ni(acac)₂, NiBr₂, NiBr₂^«3H₂0, NiBr₂»xH₂0, Ni(acac)₂^«4H₂0 and Ni(OCOCH₃)2.4H₂0; or other Ni(O-IV) species, such as Ni(II) species.

Sheet 1 of 4

7. The composition of Claim 5, wherein the palladium salt is selected from the group consisting of Pd(OAc)₂, PdCl₂, Pdl₂, PdBr₂, Pd(CN)₂, Pd(N0₃)₂ and PdS0₄; or any Pd(O-IV) species, such as a Pd(II) species.

8. The composition of Claim 5, wherein the copper salt is selected from the group consisting of CuBr, CuCl, Cu(N0₃)₂, Cul, CuS0₄, CuOAc, CuS0₄ 5 H₂0, Cu/C, Cu(OAc)₂, CuOTf C₆H₆ (OTf is trifluoromethanesulfonate) and [Cu(NCCH₃)₄][PF₆].

9. The composition of any one of Claims 1 to 8, wherein the iron salt has a purity of less than 99.999% and the iron salt is doped with a palladium salt or a nickel salt, or a

combination thereof, at 5,000 ppm, 3,000 ppm, 1,000 ppm, 500 ppm, 300 ppm, 200 ppm, 100 . ppm, 90 ppm or 80 ppm or less.

10. The composition of any one of Claims 1 to 9, wherein the source of iron is selected from the group consisting of FeCb or a Fe(II) or Fe(III) salts.

11. The composition of any one of Claims 1 to 10, wherein the surfactant is selected from the group consisting of TPGS-350-M, TPGS-550-M, TPGS-750-M, TPGS-1,000-M, TPGS- 2000-M, Triton X-100, TPGS (polyoxyethanyl-a-tocopheryl succinate), TPGS-400-1000 (D- alpha-tocopheryl polyethylene glycol 400-1000 succinate), wherein the tocopheryl is the natural tocopherol isomer or the un-natural tocopherol isomer; Nok, Pluronic, Poloxamer 188, Polysorbate 80, Polysorbate 20, Vit E-TPGS, Solutol HS 15, PEG-40 Hydrogenated castor oil (Cremophor RH40), PEG-35 Castor oil (Cremophor EL), Triton X-100, all Brij surfactants, ionic surfactants (e.g., SDS), PEG-8-glyceryl capylate/caprate (Labrasol), PEG- 32-glyceryl laurate (Gelucire 44/14), PEG-32-glyceryl palmitostearate (Gelucire 50/13);

Polysorbate 85, Polyglyceryl-6-dioleate (Caprol MPGO), Mixtures of high and low HLB emulsifiers; Sorbitan monooleate (Span 80), Capmul MCM, Maisine 35-1, Glyceryl monooleate, Glyceryl monolinoleate, PEG-6-glyceryl oleate (Labrafil M 1944 CS), PEG-6- glyceryl linoleate (Labrafil M 2125 CS), Oleic acid, Linoleic acid, Propylene glycol monocaprylate (e.g. Capmul PG-8 or Capryol 90), Propylene glycol monolaurate (e.g., Capmul PG-12 or Lauroglycol 90), Polyglyceryl-3 dioleate (Plurol Oleique CC497), and Polyglyceryl-3 diisostearate (Plurol Diis stearique), or combinations thereof^

12. The composition of any one of Claims 1 to 11, wherein the reducing agent is selected from the group consisting of a Grignard reagent or a hydride reagent.

13. The composition of Claim 12, wherein the Grignard reagent is selected from the group consisting of MeMgCl, EtMgCl, PrMgCl, BuMgCl, vinylMgCl, PhMgCl, MeMgBr, EtMgBr, PrMgBr, BuMgBr, vinylMgBr and PhMgBr, or a mixture of two or more

Sheet 2 of 4 Grignard reagents.

14. The composition of Claim 13, wherein the reducing agent is selected from the group consisting of NaBH₄, LiBH₄, KBH₄, NaBH₄-KCl, LiAl¾, LiAlH(OEt)₃, LiAlH(OMe)₃, LiAlH(0-iBut)₃, sodium bis(2-methoxyethoxy)aluminum hydride (Red-Al), LiBHEt₃,

NaBH₃CN, BH₃ and diisobutylaluminum hydride (DIBAL-H or iBu₂AlH); or any silanes (e.g., Et₃SiH, PMHS, etc ...); or dihydrogen formate or ammonium formate.

15. The composition of any one of Claims 1 to 14, wherein the solvent or cosolvent is selected from the group consisting of THF, DMF, toluene, xylenes, 2-methyl-THF, diethyl ether, 1,4-dioxane, acetonitrile, MTBE, PEG, MPEG, MeOH, EtOH, PrOH, i-PrOH, nBuOH, sBuOH, i-PrOAc and ethyl acetate, wherein the solvent or co-solvent is present in 1-3 % vol/vol or from about 0.01-50 % vol/vol relative to water.

16. A method for performing a cross coupling reaction between a first coupling substrate of the formula I with a second coupling substrate of the formula II in a reaction condition sufficient to form the coupled roduct of the formula III:

I Π 111 wherein:

X is selected from the group consisting of CI, Br and I and pseudo halides;

Y is selected from the group consisting of B(OH)2, B(OR)₂, cyclic boronates, acyclic boronates, B(MIDA),Bpin, BR(OR) and BF₃K, where R is selected from methyl, ethyl, propyl, butyl, isopropyl, ethylene glycol, trimethylene glycol, a cyclic array attaching R to -OR and pinacol; each of the groups '*--·' and j_s independently selected from the group consisting of an alkene or a substituted alkene, a cycloalkene or a substituted cycloalkene, an alkyne or a substituted alkyne, an aryl or a_suhstituted ary and a-heteroaryl or a substituted heteroaryl;

the method comprising:

i) forming a composition of any one of Claims 1 to 19, in which the partners I and II are solubilized in water, and an organometallic complex comprising iron nanoparticles,

Sheet 3 of 4 wherein another metal is present in less than 50,000 ppm relative to the limiting substrate of the formula I or formula II, wherein the metal, other than Pd, is selected from the group consisting of Pt, Au, Ni, Co, Cu, Mn, Rh, Ir, Ru and Os or a mixture thereof;

and wherein the composition further comprises a ligand of the formula A:

wherein:

X is selected from -OR¹ or -NR'R" where R' and R" is independently selected from the group consisting of H, C uioalkyl, Cs^cycloalkyl, C6-i4ar l and C4.i2heteroaryl;

X' is selected from -OR³ or -NR'R" where R' and R" is independently selected from the group consisting of H, C i-ioalkyl, C₃.6cycloalkyl, C6-i₄aryl and C_4-i2heteroaryl;

each R¹ and R³ is independently selected from a group consisting of C uioalkyl, C3_ ₆Cycloalkyl, C6.i₄aryl and C4_i2heteroaiyl;

R² is selected from the group consisting of C _MOalkyl, C_3-6cycloalkyl, C_6-i₄aryl and substituted C^aiyl and C4_i₂heteroaryl;

R⁴ is H or is selected from the group consisting of -OC i-ioalkyl, C i.ioalkyl, C3. ₆cycloalkyl, -SR⁸, -NR⁸R⁹, C6-i₄aryl and C₄-i2heteroaryl;

each R⁵ and R⁶ is H or R⁵ and R⁶ together with the aryl group to which they are attached to form a substituted or unsubstituted aromatic ring or heteroaromatic ring;

R⁷ is H or is selected from the group consisting of -OQ.joalkyl and C₁_ioalkyl, -SR⁸, - NR⁸R⁹, C6-i4aryl and C4-i2heteroaryl; and

each R and R is independently H or C uioalkyl; and

ii) contacting the first coupling substrate with the second coupling substrate in water under a condition sufficient to form a product mixture comprising a cross coupling product of the formula III.

Sheet 4 of 4