Specific insertion reactions of a germylene, stannylene and plumbylene into the unique P–P bond of the hexaphospha-pentaprismane cage, P6C4tBu4: Crystal and molecular structures of P6C4tBu4ER2 (E = Ge, Sn, R = N(SiMe3)2; E = Pb, R = (C6H3(NMe2)2 -2,6)

Abstract

Treatment of the cage compound P6C4(t)Bu4 with M(N(SiMe3)2)2 (M = Ge or Sn) or Pb(C6H3(NMe2)2- 2,6) at room temperature results in their specific insertion into the P-P bond connecting the two 5-membered P3C2(t)Bu2 rings. The products were fully characterised by multinuclear NMR spectroscopy and single crystal X-ray diffraction studies.

Spontaneous vs. Base‐Induced Dehydrochlorination of Group 14 ortho‐Carboranylamidinates

“…[18] In 1-6, the E-C-(carborane) separations are comparable with those in other group 14 organyl compounds, [24][25][26][27][28][29][30] while the E-N separations are considerably larger than those observed for classical covalent E-N bonds. [26,30,31] Within the amidine fragment, the C3-N1 separation is 126-131 pm, while the C3-N2 bond is slightly longer, at 132-137 pm. Thus in the HL -ligand, the π-electron density is probably located between the amidine C atom and the coordinated N atom, and the E-N contact should be described as a secondary coordinative interaction, rather than a covalent bond.…”

“…In particular, the Ge-N contact is strongly reduced from 204.8(2) pm to 180.0(3) pm, which corresponds to a strong covalent bond. [26,30] Figure 3. Molecular structure of 8 in the crystal.…”

“…In accordance with the lighter homologues 8-10, the Sn-N interaction can therefore be described as a strong covalent bond. [30,31] The nature of the E-N bond in the R 2 ECl[HL]-type compounds 8-11 fits to the bonding situation within the amidinate moiety. The C3-N1 bond is in the range of a single bond, with approx.…”

The role of the bis-trimethylsilylamido ligand, [N{SiMe3}2]−, in main group chemistry. Part 2: Structural chemistry of the metallic p-block elements

“…The germylene (and stannylene Sn(N{SiMe 3 } 2 ) 2 ) were also shown to insert into the unique P P bond joining the two five-membered rings of the hexaphosphapentaprismane, P 6 C 4 (t-Bu) 4 . [71] The products (68, Fig. 9; 69) showed a distorted tetrahedral geometry for the group 14 element, with P-E-P angles ∼90 • .…”

“…The resultant compound was structurally characterized as the 15-membered ring containing two 'Ge(N{SiMe 3 } 2 ) 2 ' units and two PTAD rings (70). A series of multidentate amino-and amino(ether)-ligands have been used to stabilize germylenes (and stannylenes/plumbylenes) containing the bis-trimethylsilyl ligand (71)(72)(73)(74)(75)(76) [73,74]. In the case of the germanium and tin compounds incorporating the aza-15-crown-5 group as the nitrogen substituent, the heterobimetallic complexes containing LiOTf were obtained (77, Fig.…”