Synthesis and Solid‐State Structure of a Metal Complex of a Diphosphineimine

Abstract

Ein stabilisierender Einfluss: Heterocyclische Diaminophosphine können Diphosphinimine ausreichend stabilisieren, um die Synthese von Metallkomplexen zu ermöglichen. Ein kinetisch stabiles Diphosphinimin wurde isoliert, und seine Koordinationschemie wurde anhand der Synthese von Molybdän‐ (siehe Bild) und Nickelkomplexen mit solchen PPN‐Liganden untersucht.

The crystal structure of 2-chloro-1,3-bis(2,4,6-trimethylphenyl)-4,4-dimethyl-1,3,2λ3,4-diazaphosphasiletidine

“…The unusually acute N1-Si1-N2 angle in the title compound is associated with Si-N distances of 1.7436(17) Å (Si1-N1) and 1.7445(17) Å (Si1-N2). The latter are remarkably longer than the value reported for a Si-N single bond (1.724(4) Å [13]), but correspond to those in related cyclodisilazanes [14][15][16][17][18][19][20][21][22]. Consequently, the P-N bonds are shorter than expected for a single bond (1.6857(17) Å (P1-N1) and 1.6854(17) Å (P1-N2) vs. 1.704(4) Å [13]).…”

Crystal structure of 2-chloro-1,3-di-tert-pentyl-4,4-diphenyl-1,3,2λ 3,4-diazaphosphasiletidine, C22H32ClN2PSi

“…Phosphorus and silicon atoms bear the main ring strain (N1-Si1-N2 82.89(8)°; N3-Si2-N4 82.76(7)°and N1-P1-N2 85.90(7)°; N3-P2-N4 85.75(7)°). The Si-N bond lengths (Si1-N1 1.7392(15) Å, Si1-N2 1.7418(16) Å; Si2-N3 1.7387(15) Å, Si2-N4 1.7427(15) Å) exceed the expected lenght of a Si-N single bond (1.724(4) Å [9]) but correspond to those in related cyclosilazanes [7,[10][11][12][13]. In contrast, the P-N distances are shorter (P1-N1 1.6928(15) Å, P1-N2 1.6889(18) Å; P2-N3 1.6932(15) Å, P2-N4 1.6891(16) Å) than reported for a typical single bond (1.704(4) Å [9]), but they also correspond to those in the first structurally characterized chlorosubstituted diazaphosphasiletidine [7].…”