Synthesis and Reactivity of Low‐Valent Group 14 Element Compounds 

Abstract

Abstract:The tetravalent germanium and tin compounds of the general formulae Ph*EX 3 (Ph* = 2,6-Trip 2 -C 6 H 3 , Trip = C 6 H 2 iPr 3 -2,4,6; E = Sn, X = Cl (1a), Br (1b); E = Ge, X = Cl

Stabilization of a Diphosphagermylene through pπ–pπ Interactions with a Trigonal‐Planar Phosphorus Center

“…[5,13] The two phosphorus centers in 2 are distinctly different: while P2 adopts a typical trigonal pyramidal geometry (sum of angles at P2 = 311.538), with its lone pair directed towards the rear of the molecule, P1 is essentially planar (sum of angles at P1 = 358.358) and the C1-P1-C13 and P1-Ge-P2 planes are nearly coincident. Furthermore, while the GeÀP2 distance (2.3823 (12) ) is similar to previously reported Ge II À P distances, [5][6][7] the Ge À P1 distance is approximately 6 % shorter (2.2337 (11) ). This is consistent with a significant degree of multiple bond character in the GeÀP1 bond (IV, Scheme 1); for comparison, the GeÀP distance in [CH{MeCN(Dipp)} 2 ]Ge[P(SiMe 3 ) 2 ] (3) is 2.3912(8) .…”

“…[4] It is, perhaps, surprising then that the corresponding P-substituted species (diphosphatetrylenes; (R 2 P) 2 E) [5][6][7] and their carbene homologues (PHCs) [8] are rather less well established. This, at least in part, may be attributed to the high energetic barrier to achieving the optimum planar configuration at phosphorus that would enable efficient pp-pp overlap between the phosphorus lone pair and the vacant p-orbital on the adjacent Group 14 element center (II).…”

[{2,6‐(Me2NCH2)2C6H3}Sn(μ‐OH)W(CO)5]2: A Transition‐Metal‐Coordinated Organotin(II) Hydroxide

“…The tin atom is five-coordinate and shows a strongly distorted trigonal-bipyramidal configuration with the N(1) and O(1A) atoms occupying the axial positions and the C(1), O(1A), and W(1) atoms occupying the equatorial positions. The N(1)-Sn(1) distance of 2.501(7) Å is slightly shorter than the N-Sn distances found in the corre- 3 A [8] B [17] C [9] Sn (1) [13] Similar to the latter compound, in which the second nitrogen atom does not coordinate to the tin ion but is involved in a hydrogen bond to the water oxygen atom [N···O 2.66(3) Å], the N(2) atom in compound 3 is involved in a hydrogen bond to the hydroxido oxygen atom O(1A) with an N(2)···O(1A) distance of 2.714(1) Å. The μ-hydroxido bridge is nonsymmetric with Sn(1)-O(1) and Sn(1A)-O(1) distances of 2.068(5) and 2.231(5) Å, respectively.…”

“…The μ-hydroxido bridge is nonsymmetric with Sn(1)-O(1) and Sn(1A)-O(1) distances of 2.068(5) and 2.231(5) Å, respectively. In the related compounds A-C, [8,9,17] the μ-hydroxido bridges are less nonsymmetric ( Table 2). All these Sn-O distances are, however, longer than the Sn(1)-O(5) distance of 2.001(3) Å in [(OC) 4 FeSn(OH){N(Ar)C(Me)} 2 CH]; [12] however, this compound is monomeric, and the tin atom is four-coordinate.…”

Stabilizing, non-covalent interactions in the solid state structure of novel aryltin hydrides and halogenides

“…[50][51] The compounds (2,6-Mes)PhSnCl 3 (Mes = (2,4,6-Me)Ph) and Ph*SnCl 3 (Ph* = (2,6-Trip)Ph, Trip = (2,4,6-iPr)Ph) employ sterically hindered substituents containing methylated aryl moieties on the phenyl substituents and only exhibit C-H··· interactions (Table 4). More recent examples include methyl-substituted phenyl and naphthyl derivatives.…”