Hexaalkyl Phosphorous Triamide Borines

The molecular and crystal structures of the tris(dimethylamino)phosphoranes (Me2N)3P–X (X = BH3, CH2, NH or O)

“…In a paper from 1960 describing the synthesis and chemical properties of (Me 2 N) 3 PBH 3 its high stability even to steam is attributed to stabilisation of the B-H bonds by interaction with empty d orbitals at phosphorus. 13 If such an interaction took place, one should expect a compressed P-B-H angle, and indeed the in plane P-B-H angle is only 100.9Њ (the other two 109.1) according to the calculations (note that the crystal structure values are different, but their significance can be doubted). This value is similar to those of H 3 P-BH 3 [103.6(2)Њ] and MeH 2 P-BH 3 [102.9(6) and 104.2(10)Њ].…”

Coordination chemistry of cyclamphosphorane. Access to transition-metal cyclamphosphoranides. Crystal and molecular structure of dicarbonylcyclopentadienylmolybdenum cyclamphosphoranide complex

“…The stabilizing of a P-N cycle is notable in view of the low basicity usually displayed by phosphorus-bound nitrogen atoms. 26 This occurrence certainly results in great part from the approach used in which both phosphorus and nitrogen were coordinated to the metal before being bound together. The formation of this bridge is accompanied by a lengthening of the P-N bond (1.85 Á) with respect to "normal" >P-N( single bonds.…”