A Fischer-type silylene complex of platinum: [trans-(Cy3P)2(H)Pt:Si(SEt)2]BPh4

Dispersion Forces and Counterintuitive Steric Effects in Main Group Molecules: Heavier Group 14 (Si–Pb) Dichalcogenolate Carbene Analogues with Sub-90° Interligand Bond Angles

“…The average Si-S distance in silylenes 2 (2.137(1) Å) and 3 (2.089(9) Å) are shorter than in 1 (2.158(3) Å) but are closer to those found in Tilley's bisthiolatosilylene platinum complex, trans-(Cy3P)2Pt(H)Si(SEt)2OTf (2.092(4) and 2.074(4) Å). 34 However, S-Si-S angles in 1-3 are all significantly narrower by more than 17°. Likewise, the Ge-S distances and S-Ge-S angles in germylenes 4-7 are both longer (ca.…”

The reaction of the group-13 alkyls ER3 (E=Al, Ga, In; R=CH2t-Bu, CH2 SiMe3) with the platinum-complex [(dcpe)Pt(H)(CH2t-Bu)]

“…For this reason it seems to be interesting to elucidate the possibility of the presence of Pt-E dppp interactions. A comparison could be drawn to the isovalence electronic platinum silylene complex fragment [(PCy 3 ) 2 (H)Pt@Si(SEt) 2 ] + reported by Tilley and co-workers [22,23] some time ago with an as well nearly orthogonal arrangement of the Si(SR) 2 and the L 3 Pt plane. Theoretical calculations on the basis of this system reveal a good overlap of the Si p orbital and the Pt orbitals of suitable symmetry.…”

“…Our L 3 Pt-ER 2 species does not posses p-donor ligands at the group 13 metal centre E. So, the contribution of some Pt ! E back donation is a reasonable question, similarly to the situation of the silylene complex ½Cp à ðPMe 3 Þ 2 Ru@SiMe 2 BPh F 4 [22]. However, the characterization of the Pt-E bonding situation affords a detailed qualitative and quantitative analysis of this problem via modern quantum chemical methods.…”

Transition‐Metal Complexes [(PMe3)2Cl2M(E)] and [(PMe3)2(CO)2M(E)] with Naked Group 14 Atoms (E=C–Sn) as Ligands; Part 1: Parent Compounds

“…The first synthesis of a N-heterocyclic carbene [9] was soon followed by isolation of the silicon, [10] germanium, [11] and tin [12] homologues. It took several years after the first structurally characterized transition metal complexes with a carbene ligand were reported by Fischer and Maasbçl, [13] and Schrock [14] before metal complexes with germylene, [15] stannylene, [16] and, more recently, silylene [17] ligands were prepared. A similar time evolution was observed for the triply bonded species.…”