Gregory L. Hillhouse

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Reaction of the N-tosylaziridines (p-CH(3)C(6)H(4)SO(2))NCH(2)CHR (1a, R = H; 1b, R = Me; 1c, R = n-Bu; 1d, R = i-Pr) with (bpy)Ni(cod) (2; bpy = 2,2'-bipyridine; cod = 1,5-cyclooctadiene) or (bpy)NiEt(2) (3) results in elimination of cod or butane from 2 and 3, respectively, and oxidative addition of an aziridine C-N bond to give the azametallacyclobutane(More)
The reactions of hydrochloric and triflic acids with the five-coordinate nitrosyl complexes trans-Re(CO)(2)(NO)(PR(3))(2) (2a, R = Ph; 2b, R = Cy) have been investigated. Reaction of anhydrous HCl with 2 results in a formal protonation of the nitrosyl ligand and addition of chloride to the metal, giving the neutral nitroxyl complex(More)
Reaction of the d9-d9 Ni(I) monochloride dimer, [(IPr)Ni(mu-Cl)]2 (1), with NaN(SiMe3)2 and LiNHAr (Ar = 2,6-diisopropylphenyl) gives the novel monomeric, 2-coordinate Ni(I) complexes (IPr)Ni{N(SiMe3)2} (2) and (IPr)Ni(NHAr) (3). Reaction of 2 with Cp2Fe+ results in its 1-e- oxidation followed by beta-Me elimination to give a base-stabilized iminosilane(More)
1-Adamantyl- and mesitylazide react with (dtbpe)Ni=CPh(2) (1; dtbpe = 1,2-bis(di-tert-butylphosphino)ethane) at ambient temperature to give the ketimines RN=CPh(2) (2a, R = Mes; 2b, R = Ad) in high yield. Kinetic studies for the reaction of 1 with N(3)Ad yield activation parameters of DeltaH(double dagger) = +8(+/-1) kcal/mol and DeltaS(double dagger) =(More)
The synthesis and characterization of two new carbene complexes, (dtbpe)Ni═CH(dmp) (1; dtbpe = 1,2-bis(di-tert-butylphosphino)ethane; dmp = 2,6-dimesitylphenyl) and (dippn)Ni═CH(dmp) (2; dippn = 1,8-bis(di-iso-propylphosphino)naphthalene), are described. Complexes 1 and 2 were isolated by photolysis of the corresponding side-bound diazoalkane complexes,(More)
An unusual family of three-coordinate, d(8) and d(9) nickel phosphido and phosphinidene complexes containing the chelating 1,2-bis(di-tert-butylphosphino)ethane (dtbpe) ligand and a terminal PR(2)(-) or PR(2-) ligand have been prepared. The complexes (dtbpe)Ni[P(t-Bu)(2)] (2), [(dtbpe)Ni[=P(t-Bu)(2)](+)][PF(6)(-)] (3), [(dtbpe)Ni[=P(H)(dmp)](+)][PF(6)(-)](More)
The synthesis of the first Cu2(m-S) complex, {(IPr*)Cu}2(m-S) (IPr* 1⁄4 1,3-bis(2,6-(diphenylmethyl)-4methylphenyl)imidazol-2-ylidene; 1), has been accomplished via three synthetic routes: (1) salt metathesis between (IPr*)CuCl and Na2S; (2) silyl-deprotection reaction between (IPr*)Cu(SSiMe3) and (IPr*)CuF; and (3) acid–base reaction between (IPr*)Cu(SH)(More)
Kinetic and DFT computational studies reveal that the reaction of {(IPr)Ni(μ-S)}2 (1, IPr = 1,3-bis(2,6-diisopropyl-phenyl)imidazolin-2-ylidene) with dihydrogen to produce {(IPr)Ni(μ-SH)}2 (2) proceeds by rate-limiting heterolytic addition of H2 across a Ni-S bond of intact dinuclear 1, followed by cis/trans isomerization at Ni and subsequent H migration(More)
An exceptionally low coordinate nickel imido complex, (IPr*)Ni═N(dmp) (2) (dmp = 2,6-dimesitylphenyl), has been prepared by the elimination of N2 from a bulky aryl azide in its reaction with (IPr*)Ni(η6-C7H8) (1). The solid-state structure of 2 features two-coordinate nickel with a linear C−Ni−N core and a short Ni−N distance, both indicative of(More)