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Chemistry of Three-Coordinate Nickel with Multiply-Bonded Ligands

• Perparation of stable alkyl complexes of Ni(I) and their one-electron oxidation to Ni(II) complex cations.  K. D. Kitiachvili, D. J. Mindiola, and G. L. Hillhouse, J. Am. Chem. Soc., 126, 10554-10555 (2004). 

• Group transfer from nickel imido, phosphinidene, and carbene complexes to ethylene with formation of aziridine, phosphirane, and cyclopropane products.  R. Waterman and G. L. Hillhouse, J. Am. Chem. Soc., 125, 13350-13351 (2003). 

 
• Formation of phosphirenes by phosphinidene group-transfer reactions from (dtbpe)Ni=P(dmp) to alkynes.  R. Waterman and G. L. Hillhouse, Organometallics, 22, 5182-5184 (2003). 

 
• Synthesis of 1,2-bis(di-tert-butylphosphino)ethane (dtbpe) complexes of nickel: Radical coupling and reduction reactions promoted by the nickel(I) dimer [(dtbpe)NiCl]₂. D. J. Mindiola, R. Waterman, D. M. Jenkins, and G. L. Hillhouse, Inorg. Chim. Acta, 345, 299-308 (2003). 

• Isocyanate and carbodiimide synthesis by nitrene-group-transfer from a nickel(II) imido complex. D. J. Mindiola and G. L. Hillhouse, J. Chem. Soc., Chem. Commun., 1840-1841 (2002). 

• Synthesis, structure, and reactions of a three-coordinate nickel-carbene complex, {1,2-bis(di-tert-butylphosphino)ethane}Ni=CPh₂. D. J. Mindiola and G. L. Hillhouse, J. Am. Chem. Soc., 124, 9976-9977 (2002). 

• Monomeric phosphido and phosphinidene complexes of nickel.  R. Melenkivitz, D. J. Mindiola, and G. L. Hillhouse, J. Am. Chem. Soc., 124, 3846-3847 (2002). 

• Terminal amido and imido complexes of three-coordinate nickel.  D. J. Mindiola and G. L. Hillhouse, J. Am. Chem. Soc., 123, 4623-4624 (2001). 

Coordination Chemistry of Nitroxyl (HN=O) and Diazene (HN=NH)

A new route to coordination complexes of nitroxyl (HN=O) via insertion reactions of nitrosonium triflate with transition-metal hydrides. R. Melenkivitz, J. S. Southern, G. L. Hillhouse, T. E. Concolino, L. M. Liable-Sands, and A. L. Rheingold, J. Am. Chem. Soc., 124, 12068-12069 (2002). 

Synthesis, structure, and reactions of a nitroxyl complex of iridium(III), cis,trans-IrHCl₂(NH=O)(PPh₃)₂. R. Melenkivitz and G. L. Hillhouse, J. Chem. Soc., Chem. Commun., 660-661 (2002). 

Chemistry of coordinated nitroxyl. Reagent-specific protonations of trans- Re(CO)₂(NO)(PR₃)₂ (R = Ph, Cy) that give the neutral nitroxyl complexes cis,trans- ReCl(CO)₂(NH=O)(PR₃)₂ or the cationic hydride complex [trans,trans- ReH(CO)₂(NO)(PPh₃)₂⁺][SO₃CF₃^-].  J. S. Southern, M. T. Green, G. L. Hillhouse, I. A. Guzei and A. L. Rheingold, Inorg. Chem., 40, 6039-6046 (2001). 

Preparation of a nitroxyl (HN=O) complex of rhenium by selective oxidation of coordinated hydroxylamine.  J. S. Southern, G. L. Hillhouse, and A. L. Rheingold, J. Am. Chem. Soc., 119, 12406-12407 (1997). 

Reactions of coordinated diazene in rhenium and tungsten complexes.  Deprotonation of ligated NH=NH and subsequent H-migration to carbonyl ligands to give metal formyls.  T.-Y. Cheng, J. C. Peters, and G. L. Hillhouse, J. Am. Chem. Soc., 116, 204-207 (1994). 

Hydroxylamine, hydrazine, and diazene as unidentate ligands in osmium and ruthenium complexes.  T.-Y. Cheng, A. Ponce, A. L. Rheingold, and G. L. Hillhouse, Angew. Chem., Int. Ed. Engl., 33, 657-659 (1994). 

Syntheses and reactions of hydrazine and diazene complexes of tungsten.  The first example of monodentate coordination of NH=NH.  M. R. Smith III, T.-Y. Cheng, and G. L. Hillhouse, J. Am. Chem. Soc., 115, 8638-8642 (1993). 

Atom and Group Transfer Chemistry involving Organonickel Complexes

•  Interactions of aziridines with nickel complexes:  Oxidative-addition and reductive-elimination reactions that break and make C-N bonds.  B. L. Lin, C. R. Clough, and G. L. Hillhouse, J. Am. Chem. Soc., 124, 2890-2891 (2002). 

• Sulfur-atom transfer from elemental sulfur to nickel-carbon bonds as a new route to reactive nickel(II) thiolates.  R. Han and G. L. Hillhouse, J. Am. Chem. Soc., 120, 7657-7658 (1998). 

• Formation of a substituted tetrahydrofuran by the formal [2+2+1] coupling of an oxygen atom with two olefins at a nickel center.  K. Koo and G. L. Hillhouse, Organometallics, 17, 2924-2925 (1998). 

• Carbon-oxygen reductive elimination from nickel(II) oxametallacycles and factors that control formation of ether, aldehyde, alcohol, or ester products.  R. Han and G. L. Hillhouse, J. Am. Chem. Soc., 119, 8135-8136 (1997). 

• Indoline synthesis via coupling of phenethyl Grignard reagents with organoazides mediated by (alkylphosphine)nickel(II) complexes.  K. Koo and G. L. Hillhouse, Organometallics, 15, 2669-2671 (1996). 

• Oxygen-atom transfer from nitrous oxide (N=N=O) to nickel alkyls.  Syntheses and reactions of nickel(II) alkoxides.  P. T. Matsunaga, J. C. Mavropoulos, and G. L. Hillhouse, Polyhedron, 14, 175-185 (1995). 

• Oxygen-atom transfer from nitrous oxide to an organonickel(II) phosphine complex.  Syntheses and reactions of new nickel(II) aryloxides and the crystal structure of (Me₂PCH₂CH₂PMe₂)Ni(O-o-C₆ H₄CMe₂CH₂).  K. Koo, G. L. Hillhouse, and A. L. Rheingold, Organometallics, 14, 456-460 (1995). 

• Carbon-nitrogen bond formation by reductive elimination from nickel(II) amido alkyl complexes.  K. Koo and G. L. Hillhouse, Organometallics, 14, 4421-4423 (1995). 

• Reactions of organoazides with nickel alkyls.  Syntheses and reactions of nickel(II) amido complexes.  P. T. Matsunaga, C. R. Hess, and G. L. Hillhouse, J. Am. Chem. Soc., 116, 3665-3666 (1994). 

• Thianickelacycles by ring-opening reactions of cyclic thioethers and their subsequent carbonylation to thioesters.  P. T. Matsunaga and G. L. Hillhouse, Angew. Chem., Int. Ed. Engl., 33, 1748-1749 (1994). 

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