Multiple Bonding Between Silicon and Molybdenum: A Transition‐Metal Complex with Considerable Silylyne Character

Abstract

radiation, l ¼ 0.71073 ä, m ¼ 0.269 mm À1 , T ¼ À100 K. 25 627 data (13 056 unique, R int ¼ 0.0146, q < 27.528) were collected on a Bruker SMART APEX CCD X-ray diffractometer. The structure was solved by direct methods and refined by full-matrix least-squares on F 2 values of all data (G. M. Sheldrick, SHELXTL Manual) to give wR2 ¼ 0.0824, conventional R ¼ 0.0313 for F values of 12 747 reflections, S ¼ 1.037 and 773 parameters. Residual electron density max/min 0.448/ À0.232 e ä À3 . CCDC-183413 (1) contains the supplementary [*] Prof.

News from Silicon: An Isomer of Hexasilabenzene and A Metal–Silicon Triple Bond

“…The experimental molecular structure of complex 2 resembles an almost C s ‐symmetric three‐legged piano stool with a very short MoSi bond of 222.4 pm (Scheme ). A similar short MoSi bond was found previously only in the complex cation salt 21 [B(C 6 F 5 ) 4 ] (MoSi: 221.9 pm) isolated by Mork and Tilley 20. In this case, the MoSi bond is bridged by an additional three‐center MoHSi bond.…”

Hydrido(hydrosilylene)tungsten Complexes with Strong Interactions between the Silylene and Hydrido Ligands

“…[1] Since the late 1980s a number of base-stabilized and base-free silylene complexes have been synthesized and characterized. [1][2][3][4][5][6][7][8][9][10][11] Among these complexes, those that bear H atoms on the silylene ligand are particularly interesting because the Si À H bond could diversify the reactivity of the M=Si bond through its possible reactions, such as a-elimination, oxidative addition, and hydrosilylation. However, donor-free silylene complexes of this type only became known quite recently.…”

An Air‐Stable Heterobimetallic Si2M2 Tetrahedral Cluster

“…The chemistry of transition‐metal silylidyne complexes has a short, yet spectacular history. The arguably first silylidyne complex [Cp*(dmpe)(H)MoSiMes] (dmpe=PMe 2 CH 2 CH 2 PMe 2 ) was reported by Tilley and Mork in 2003 . Shortly after, when the role of the NHC in stabilizing low‐valent silicon(II) species had been recognized, a genuine Mo≡Si triple‐bonded complex was isolated by the group of Filippou using this elegant synthetic approach .…”

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