Notizen / Notes. Eine neue Bildungsweise der Phosphor – Phosphor‐Bindung. Kristallstrukturanalyse von Tetramethyldiphosphanmonosulfid

A New Mode of Formation of a Phosphorus ‐ Phosphorus Bond. X‐ray Crystal Structure of Tetramethyldiphosphane Monosulfide Tetraphenyldiphosphane monosulfide ( 7 ) was formed during an attempt to synthesize the diphenylphosphino‐substituted thioureas 5 and 6 by the reaction of thiourea ( 1 ) or N,N ′‐bis‐(trimethylsilyl)thiourea ( 2 ) with chlorodiphenylphosphane. The attempted distillation of the dimethylphosphino‐substituted N,N ′‐dimethylthiourea 9 furnished tetramethyldiphos‐phane monosulfide ( 10 ). These reactions provide a new mode of formation of phosphorus – phosphorus bonds. – According to an X‐ray analysis, 10 crystallizes in the space group P 2 1 /n. The molecule adopts a trans configuration, with the S atom antiperiplanar to the lone pair.