Isolation of a Hydrogen-Bridged Bis(silylene) Tungsten Complex: A Snapshot of a Transition State for 1,3-Hydrogen Migration

Abstract

A hydrogen-bridged bis(silylene) complex, which can be viewed as a snapshot of a transition state for 1,3-hydrogen migration, was isolated, and its unprecedented WSi2H four-membered-ring structure with a short diagonal Si-Si distance was revealed by X-ray crystallography. NMR studies including determination of the W-Si, Si-Si, and Si-H coupling constants and theoretical calculations suggest that a novel multicenter bond is formed in the WSi2H system, in which the bridging hydrogen takes on a hydridic nature.

Direct and Indirect Pathways of CdTeSe Magic-Size Cluster Isomerization Induced by Surface Ligands at Room Temperature

“…We have shown for the first time how colloidal semiconductor MSCs isomerize at low temperatures under external chemical stimuli (Scheme ). Like organic molecules, − the isomerization described here proceeds along intracluster (pathway 1) and intercluster (pathway 2) pathways. Also, as for metal clusters, , it is the surface ligand that induces the isomerization.…”

“…Therefore, the present study brings more fundamental insights on the two pathways of MSC isomerization, together with more implications (as discussed before the Conclusion in Figures S10-1–S10-4). As for organic molecules, − the MSC isomerization occurs following intracluster (pathway 1) and intercluster (pathway 2) pathways. Furthermore, like metal clusters, , the isomerization here is induced by surface ligands; isomerization instead of quasi-isomerization or pseudoisomerization is used in the present study.…”

“…The reactions that chemically transform the QDs have similarities with traditional organic reactions, although isomerization is not addressed . Nonetheless, isomerization is ubiquitous in organic molecules. − When a molecule of an open-chain unsaturated hydrocarbon isomerizes into another open-chain hydrocarbon or a cyclic one, the process can be reversible or not. Such isomerization may involve a shift of one atom (such as hydrogen) or a group of atoms (such as −CH 3 ) from one carbon atom to another.…”

Schrock‐TypeSilylidenesandGermylidenesFound Among the Silylene and Germylene Complexes of the Early and Mid‐Transition Metals

“…Tobita and coworkers described also a series of the intramolecularly donorstabilized tungsten silylene complexes. They include Cp*-(OC) 2 [2-Me 2 NÀ C 6 H 4 ]W=SiMe 2 in which silicon center is coordinated by Me 2 N-group of aromatic substituent, [79] Cp*-(OC) 2 (H)W=Si(H)[C(SiMe 3 ) 3 ] which manifested a significant interligand interaction between the silylene and hydrido ligands, [80] and hydrogen-bridged tungsten bis(silylene) complex Cp*(OC) 2 W{Me 2 Si *** H *** Si(Me) t Bu} [81] . All these complexes were uniformly prepared by the photochemical reaction of Cp*-(OC) 3 W(Me) and the corresponding hydrosilane, and exhibited features that are typical for the base-stabilized tungsten silylene complexes, namely: low-field 29 As the most significant achievement in the field of the tungsten silylene complexes, several base-free (that is, the least electronically perturbed) representatives were described in the past two decades.…”

Preparation and Structural Study of a Thermally Stable Bis(Disilanyl) Platinum(II) Complex

“…Oxidative addition of different types of hydrosilanes with transition metal substrates is an effective method for the synthesis of silyl complexes containing silicon-metal bonds. [1][2][3][4][5] A number of novel structures, including mononuclear and multinuclear frameworks with different valencies, have been disclosed in the past few decades. [6][7][8][9][10] Among these transition metal silyl complexes, silyl platinum complexes have been most widely investigated, which may be due to the higher stability of platinum complexes than those of the corresponding palladium and nickel complexes.…”