Stability of Trivalent Vanadium Alkyl and Hydride Supported by a Chelating Phosphinimido Ligand

Abstract

Reaction of [(Me 3 Si)NdP(Ph) 2 C(H)P(Ph) 2 dN(SiMe 3 )]VCl 2 (1) with 2 equiv of MeLi yielded the corresponding trivalent vanadium derivative [(Me 3 Si)NdP(Ph) 2 C(H)P(Ph) 2 dN(SiMe 3 )]-VMe 2 (3). Subsequent hydrogenolysis afforded the dinuclear hydride complex {[(Me 3 Si)Nd P(Ph) 2 C(H)P(Ph) 2 dN(SiMe 3 )]V} 2 (µ-H) 2 ( 4), where reduction of the metal center to the divalent state had occurred. Hydrogenolysis of solutions of 1 previously treated with lower than stoichiometric amounts of MeLi afforded the two mixed-valent V(II)/V(III) hydrides 7). Hydrolysis of the divalent 4 afforded the trivalent and dinuclear {[(Me 3 Si)NdP(Ph) 2 C(H)P(Ph) 2 d(µ-N)]V(OSiMe 3 )} 2 (5), featuring migration of the Me 3 Si group from the N to the O atom of one incoming molecule of water.

(Iminophosphoranyl)(thiophosphoranyl)methane rare-earth borohydride complexes: synthesis, structures and polymerization catalysis

“…Both ligands have been extensively used in main group, 1-16 transition [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] and f-element 5,13,15,19,[35][36][37][38][39][40][41][42][43][44][45][46][47][48][49] chemistry. Both ligands have been extensively used in main group, 1-16 transition [16][17][18][19][20][21][22][23][24][25][26][27][28][29]…”

Syntheses and structures of dimeric sodium and potassium complexes of 2,6-diisopropyl-anilidophosphine borane ligand

“…1,2 Recently, there has been significant research effort in employing inorganic amines and imines to study coordination chemistry. The P-N ligand systems such as monophosphanylamides (R 2 PNR') [3][4][5][6][7] diphosphanylamides ((Ph 2 P) 2 N), 4,[8][9][10][11] phosphoraneiminato (R 3 PN), 12,13 phosphiniminomethanides ((RNPR' 2 ) 2 CH), [15][16][17][18][19][20][21][22] phosphinimin-methandiides ((RNPR' 2 ) 2 C), [23][24][25][26][27] and diimino-phosphinates (R 2 P(NR')) [28][29][30][31] are well-known as ligands and have proved their importance in transition and rare earth metal chemistry. We have recently introduced a series of phosphineamines [Ph 2 PNHR] (A) (R = 2,6-Me 2 C 6 H 3 CHPh 2 ,C P h 3 ) and their chalcogen derivatives [Ph 2 P(O)NHR] (NPO), [Ph 2 P(S)NHR] (NPS)and [Ph 2 P(Se)NHR] (NPSe) (chart 1) to the chemistry of alkali metals and the heavier alkaline earth metals.…”

Group 1 and 13 complexes of aryl-substituted bis(phosphinimino)methyls

“…The trimethylsilyl-substituted bis(phosphinimino)methane, IV, has been the subject of a number of recent publications [32][33][34][35][36][37][38], most notably in its doubly deprotonated form for the synthesis of Ôpin-cerÕ carbene complexes of the group 4 elements [39]. Use of the N-aryl substituted variants II and III however is restricted to a single account of their application as ancillary ligands for Co(II)-and Ni(II)-based olefin polymerisation catalysts [31] and our recent reports of their application in the support of three-coordinate mid and late first row (Mn-Zn) transition metal amides and alkoxides [1].…”