28069-69-4Relevant articles and documents
Synthesis and reactivity of silyl iron, cobalt, and nickel complexes bearing a [PSiP]-pincer ligand via Si-H bond activation
Wu, Siquan,Li, Xiaoyan,Xiong, Zichang,Xu, Wengang,Lu, Yunqiang,Sun, Hongjian
, p. 3227 - 3237 (2013/07/19)
The synthesis and characterization of a series of Ni, Co, and Fe complexes bearing a tridentate bis(phosphino)silyl ligand (κ3-(2-Ph 2PC6H4)2SiMeH, [PSiP]-H, 1) are reported. 1 reacted with Ni(PMe3)4 to afford the mononuclear nickel(0) complex [η2(Si-H)-PSiP]Ni(PMe3) (2). The halogeno nickel complexes [PSiP]Ni(X)(PMe3) (X = Cl (3), Br (4), I (5)) were synthesized in the reactions of 2 with Me3SiCl or MeHSiCl2, EtBr, and MeI. Complex 2 underwent ligand substitution of PMe3 by CO to give [η2(Si-H)-PSiP]Ni(CO) (6). Complex 3 reacted with NaOMe to deliver [PSiP]Ni(OMe)(PMe3) (7) through anionic ligand substitution, while the neutral ligand replacement of PMe 3 by CO in 3 afforded the rare hexacoordinate 20-electron nickel(II) complex [PSiP]Ni(Cl)(CO)2 (8). Unexpectedly, reaction of 1 with NiMe2(PMe3)3 produced the tetracoordinate nickel(0) complex [Me2PSiP]2Ni (9). The complex [Me 2PSiP]Ni(CO)2 (10) was acquired from 9 after the substitution of one [PSiP] ligand by two carbonyl ligands. 1 reacted with Co(PMe3)4 or CoCl(PMe3)3 to afford the hydrido cobalt(II) complex [PSiP]CoH(PMe3) (11) or hydrido cobalt(III) complex [PSiP]Co(H)(Cl)(PMe3) (13). Complex 12, [PSiP]Co(H)(I)(PMe3), could be obtained from the reaction of MeI with 11 or 13. Treatment of 13 with 1 equiv of MeLi or n-BuMgBr in THF resulted in the clean formation of cobalt(I) complex [PSiP]Co(PMe3)2 (14) via reductive elimination. The simple anhydrous inorganic salt NiCl 2 or CoCl2 could also react with 1 in the presence of PMe3 to form the corresponding silyl complexes 3 and [PSiP]Co(Cl)(PMe3) (15) via Si-H bond cleavage. 1 reacted with Fe(PMe3)4 to form the hexacoordinate octahedral hydrido iron(II) complex [PSiP]Fe(H)(PMe3)2 (16). The molecular structures of complexes 2-5, 10, 12, 13, 15, and 16 were determined by X-ray single crystal diffraction. 16 has excellent catalytic reactivity for the reduction of aldehydes and ketones.
Insertion of alkynes into Ni-H bonds: Synthesis of novel vinyl nickel(II) and dinuclear vinyl nickel(II) complexes containing a [P, S]-ligand
She, Lei,Li, Xiaoyan,Sun, Hongjian,Ding, Jun,Frey, Markus,Klein, Hans-Friedrich
, p. 566 - 570 (2008/10/09)
Reactions of alkynes with nickel hydride complexes bearing a [P, S]-ligand and supported by trimethylphosphine were investigated. Tetracoordinate vinyl nickel(II) complexes 3, 5, and 6 with square-monoinsertionplanar geometry were obtained by reacting phenylacetylene, trimethylsilylacetylene, and 1-hexyne with the hydrido nickel complex 1. Reaction of 1,4-bis(trimethylsilylethynyl)benzene with complex 1 proceeds as a monoinsertion and afforded complex 7, while reaction of 1,4-bis(ethynyl)benzene with 1 leads to the dinuclear vinyl nickel(II) complex 8.
Oxidative coupling of phosphinomethanides at a metal centre: P-P vs. C-C bond formation and the molecular structure of the novel bis-ylide (Me 3Si)2C=PMe2-PMe2=C(SiMe 3)2
Karsch, Hans H.,Deubelly, Brigitte,Mueller, Gerhard
, p. 517 - 518 (2007/10/02)
Metal induced coupling of [CH2PMe2]- leads to Me2PCH2CH2PMe2, whereas coupling of [C(X)(SiMe3)(PMe2)]- (X=SiMe3 or PMe2) results in P-P bond formation affording [(X)(SiMe 3)C=PMe2-]2, with a central P-P bond of length 2.278(1) A.
