Preparation and Structure of a New Dipalladium Complex with Bridging Diphenylgermyl Ligands. Diverse Reactivities of Pd(PCy₃)₂ and Pt(PCy₃)₂ toward Ph₂GeH₂

Abstract

A dinuclear palladium complex haVing bridging diphenylgermyl ligands, [{Pd(PCy 3 )} 2 (µ-HGePh 2 ) 2 ] (1), was obtained from the reaction of Ph 2 GeH 2 with [Pd(PCy 3 ) 2 ]. X-ray crystallographic results and NMR spectra of 1 reVealed coordination of the Ge ligands to two Pd centers Via a Ge-H-Pd three-center-two-electron bond and a Ge-Pd σ bond. The reaction of Ph 2 GeH 2 with [Pt(PCy 3 ) 2 ] produces the (germyl)hydridoplatinum complexes cis-[Pt(H)(GeHPh 2 )(PCy 3 ) 2 ] (cis-3) and trans-[Pt(H)(GeHPh 2 )(PCy 3 ) 2 ] (trans-3) as the kinetic and thermodynamic products, respectiVely.

Reduction of a Chelating Bis(NHC) Palladium(II) Complex to [{μ‐bis(NHC)}2Pd2H]+: A Terminal Hydride in a Binuclear Palladium(I) Species Formed under Catalytically Relevant Conditions

“…The Pd À H bond length in 2 determined from the neutron structure analysis (1.58(3) ) is typical, and is comparable to the m-HÀPd I distance in [(dipp) 2 Pd 2 (m-H)(m-CO)] + (1.531 (11) and 1.540(10) ; X-ray; dipp = 1,3-bis(diisopropylphosphino)propane). [9] A terminal hydride (1.53 (5) ) is known for the Pd II A-frame complex [(m-dppm) 2 HPd(m-Cl)PdMe] + , [10] (Pd···Pd 3.013(1) ; dppm = bis(diphenylphosphino)methane).…”

“…Pd/E bridged hydrides exist for [LPd 2 (m-HER 2 ) 2 ] n+ (E = Si, Ge, P). [11] Terminal PdÀH bond lengths in a bis-(NHC)Pd II benzoate [12] and two cationic (NHC)Pd II species [13] are 1.54(2), 1.77 (7), and 1.57(3) , respectively (all X-ray).…”

Activation of the Ge–H bond of Et3GeH in photochemical reaction with molybdenum(0) carbonyl complexes and hydrogermylation of norbornadiene

“…In comparison to H-Si bonds, the reactivity of H-Ge bonds towards W(0) and Mo(0) complexes is less well studied [6,7]. The activation of the H-Ge bond of germanes by platinum and palladium complexes is better investigated [18][19][20]. In this paper, we present studies of the activation of the H-Ge bond of triethylgermane using photochemically generated coordinatively unsaturated molybdenum(0) carbonyl complexes.…”

Bond Formation and Coupling between Germyl and Bridging Germylene Ligands in Dinuclear Palladium(I) Complexes

“…They also suggest that these changes are closely associated to their bond lengths and strengths, and that the interaction occurs in a concerted manner. The formation of a three-center-two-electron Ge À H···Ge bond as an explanation for the observed close contact of the Ge atoms can be excluded based on the analysis of the X-ray diffraction experiments [Pd-Ge2-C angles for 1 a: 106.1(2)8/104.8(2)8; 2 a: 111.56 (7) [19] or [(Me 3 P)Pd(mSiHPh 2 ) 2 Pd(PMe 3 ) n ] [n = 1, 2.691(1) ; n = 2, 2.740 (1) ]. [20] Based on X-ray and DFT results, the metal-metal bonds in the PMe 3 -containing complexes (2 a, b) are significantly more destabilized compared to those in 1 a, b.…”