Reactions of Hydrosilanes with Transition Metal Complexes

Abstract

This third review in a series involving reactions of hydrosilanes and transition metal complexes and characterization of the products covers the period 2009 thru 2013. After a brief discussion of other synthetic methods used for the formation of Si-TM complexes, Section 3 provides an extended discussion of the types of ligands and metal complexes used as reactants with hydrosilanes. The increase in use of pincer ligands in forming stable, isolable complexes is featured. Three tables list the complexes reported for primary, secondary, and tertiary silanes. Many reactions leading to SiTM complexes are initiated by loss of a ligand prior to oxidative addition of the hydrosilane or by a metathesis reaction. Structural data are tabulated for the isolated complexes and provide the Si-TM bond ranges for the elements in the "d" block. A major section on nonclassical (σ or agostic) complexes includes two general groupings with Si-H···TM and M-H···Si interactions. A section on solution processes identified by NMR spectroscopy is dominated by hydride exchange examples. A section on bonding outlines a unifying bonding description that has been proposed as well as calculations reported for Si-TM complexes, both real and hypothetical examples.

Construction of a Planar Tetrapalladium Cluster by the Reaction of Palladium(0) Bis(isocyanide) with Cyclic Tetrasilane

“…The 1 H and 13 C{ 1 H} NMR spectra of 5 are consistent with the expectation from its pseudo-C 3 symmetric structure. One singlet derived from the carbene carbon atom of the i Pr 2 IM Me moiety was observed at 194.0 ppm in the 13 [35], but it is within the range for bridging silylene ligands reported in the literature [42][43][44]. …”

“…The 29 Si{ 1 H} NMR spectrum of 4 showed a singlet at 223.1 ppm, which is comparable to those derived from the silylene moieties of 2 (191.85 and 226.63 ppm). This signal appeared at slightly lower field compared with Osakada's Pd4Si3 cluster (195 ppm) [35], but it is within the range for bridging silylene ligands reported in the literature [42][43][44]. The molecular structure of 5 is shown in Figure 2, and selected bond distances are summarized in Table 1.…”

Si–H Bond Activation of a Primary Silane with a Pt(0) Complex: Synthesis and Structures of Mononuclear (Hydrido)(dihydrosilyl) Platinum(II) Complexes

“…The P1-Pt1-P2 angle of 101.63(3)° and P1-Pt1-Si1 angle of 96.17(3)° deviated considerably from the ideal 90° of square-planar geometry. The Pt-Si bond length is 2.3458(9) Å, which is comparable to those ranging from 2.321 to 2.406 Å observed in the related mononuclear platinum(II) complexes bearing silyl ligands [1]. The hydrogen atom on the platinum atom was located in the electron density map and has a Pt-H distance of 1.59 (4) The molecular structure of 2 was determined unambiguously by X-ray crystallographic analysis, as depicted in Figure 1.…”

“…The transition metal catalyzed synthesis of functionalized organosilicon compounds gained substantial momentum during the past few decades [1]. Among these catalytic conversions, the oxidative addition of hydrosilanes with platinum(0) complexes is an efficient method for the generation of the platinum(II) hydride species, which has been proposed as a key intermediate in platinum-catalyzed hydrosilylations [2][3][4][5][6] and bis-silylations [7,8], as well as the dehydrogenative couplings of hydrosilanes [9][10][11][12][13].…”

Synthesis of a Silyl Cobalt Hydride and Its Catalytic Performance in Kumada Coupling Reactions

“…[1][2][3][4][5] Iwasawa and coworkers used pincer-type hydrido-palladium complexes to hydrocarboxylate of allenes with CO 2 . [6] At ridentate pincer-type bis(phosphino)silyl ligand [PSiP] was used by Turculet andc oworkers to synthesize ar uthenium(II)-dinitrogen complex [Ru(H)(N 2 )(PSiP-Ph)] under an itrogen atmosphere.…”