1002720-82-2Relevant academic research and scientific papers
Synthesis and characterization of neutral and cationic platinum(II) complexes featuring pincer-like Bis(phosphino)silyl ligands: Si-H and Si-Cl bond activation chemistry
Mitton, Samuel J.,McDonald, Robert,Turculet, Laura
, p. 5122 - 5136 (2010/01/06)
The synthesis and characterization of a new series of Pt(II) complexes bearing the tridentate bis(phosphino)silyl ligands [k3-(2-R 2PC6H4SiMe]- ([R-PSiP], R = Ph, Cy) are reported. The tertiary silane [Ph-PSiP]H reacted with PtCl 2(SEt2)2 to afford [Ph-PSiP]PtCl (1), which was structurally characterized. Alkyl derivatives of 1 were prepared in high yields by the reaction of 1 with either PhCH2K to afford [PhPSiP]PtCH 2Ph (2) or MeLi to afford [Ph-PSiP]PtMe (3). The X-ray crystal structure of 2-CH2Cl2 was obtained and confirmed a square-planar geometry about Pt, with the benzyl ligand positioned trans to Si. Treatment of either 2 or 3 with 1 equiv of B(C6F5) 3 in benzene solution led to the formation of the corresponding cationic species {[Ph-PSiP]Pt}+[RB(C6F5) 3]- (R = CH2Ph, 4; R = Me, 5). X-ray quality crystals of 4(OEt2) · OEt2 were grown from an Et2O solution of 4; the crystal structure of 4(OEt2) · OEt2 features an Et2O molecule coordinated to the cationic Pt center, resulting in square-planar coordination geometry at Pt. Both 4 and 5 underwent a subsequent reaction to generate [Ph-PSiP]Pt(C 6F5) (6). Treatment of 1 with 1 equiv of Li[B(C 6F5)4](OEt2)2.5 in fluorobenzene afforded {[Ph-PSiP]Pt(OEt2)}+[B(C 6F5)4]- (7(OEt2)) · Although the reaction of 1 with AlCl3 led to a mixture of products, crystallization attempts enabled the isolation of a minute quantity of fluorobenzene-solvated [Ph-PSiP]PtCl-ACl3 (1(AlCl3) · (C6H5F)2), which was crystallographically characterized and features a chloride ligand bridging the Pt and Al centers. The dicyclohexylphosphino derivative [Cy-PSiP]H reacted with PtCl2(SEt2)2 in the presence of Et3N to afford [Cy-PSiP]PtCl (8), which reacted with AgOTf to form [Cy-PSiP]PtOTf (9). Heating of either 8 or 9 for extended periods in benzene solution in the presence of amine bases did not result in benzene activation. Treatment of 8 with RLi reagents (R = Me, Ph) afforded the corresponding methyl ([Cy-PSiP]PtMe, 10) and phenyl ([Cy-PSiP]PtPh, 11) complexes, the latter of which was crystallographically characterized. As was observed for 3, compound 10 reacted with 1 equiv of B(C6F5)3 to form {[CyPSiP]Pt} +[MeB(C6F5)3]- (12), which upon heating in benzene afforded [Cy-PSiP]Pt(C6F5) (13) with loss of MeB(C6F5)2. Treatment of 8 with LiEt3BH led to the formation of [Cy-PSi(μ-H)P]Pt (14), which was identified on the basis of NMR and IR spectroscopic data as a bis(phosphino) Pt derivative of [Cy-PSiP]H that features η2-Si-H coordination involving the tethered silicon fragment. Athough complexes 2,3, and 10 did not react with an atmosphere of H2, these compounds reacted readily with 1 equiv of PhSiH3 to form the corresponding silyl complexes ([Ph-PSiP]PtSiH2Ph, 15; [Cy-PSiP]PtSiH2Ph, 16) upon loss of toluene or methane, respectively. While 2 and 3 also reacted with 1 equiv of Ph2SiHCl to form the silyl complex [PhPSiP]PtSiPh2Cl (17), 10 reacted with either Ph2SiHCl or iPr2SiHCl to form [Cy-PSiP]PtCl (8). Complex 10 also reacted with 1 equiv of Me 3SiCl to form 8 and Me4Si upon heating. Although complex 11 also reacted with hydridochlorosilanes to form 8, these reactions were significantly slower relative to 10. In contrast to 10 and 11, the η2-Si-H complex 14 reacted with 1 equiv of either PhSiH 3 or Ph2SiHCl to form the corresponding Pt silyl complexes 16 and [Cy-PSiP]RSiPh2Cl (18), with loss of H2.
Synthesis and reactivity of platinum group metal complexes featuring the new pincer-like bis(phosphino)silyl ligand [K3-(2-Ph 2PC6H4)2SiMe]- ([PSiP]): Application in the ruthenium-mediated
MacInnis, Morgan C.,Maclean, Darren F.,Lundgren, Rylan J.,Mcdonald, Robert,Turculet, Laura
, p. 6522 - 6525 (2008/10/09)
The synthesis of coordinatively unsaturated Ru, Rh, Pd, and Pt complexes supported by the new pincer-like bis(phosphino)silyl ligand [k 3-(2-Ph2PC6H4)2SiMe] - ([PSiP]) is described. In the
