Structure, bonding, and chemistry of closo-tetraphosphorus hexakis(methylimide), P4(NCH3)6, and its derivatives. I. The structures of the tetra-p-thio and tetra-p-oxo derivatives

Structure, bonding, and chemistry of closo-tetraphosphorus hexakis(methylimide), P4(NCH3)6, and its derivatives. 2. Polymorphs of the monothio derivative

“…The P-S distance, 1.92 (1) Á, is essentially the same as those found in the other S"P4(NMe)6 ( = 2, 3, 4) molecules. 3,4 There seem to be no published (=N)3P-S distances with which to compare it. It appears from data on X3PS (X = CH3, Cl, F)11 compounds that P-S distances are a function of the properties of the X groups depending perhaps on electronegativity and/or -bonding ability.…”

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

“…The addition of sulfur can be carried out stepwise to achieve the desired degree of sulfurization (142)(143)(144)(145). [80,[88][89][90][91][92][93] The addition of transition metal moieties was also realized by reactions with [Ni(CO)4] to 131 and 134, resulting in adamantanes with terminal Ni(CO)3 groups (146 and 147). [94] The ligand sphere on the phosphorous atom can also be expanded stepwise by introducing a SiMe3 group in [(PNSiMe3)4(NMe)6] (148), which Me3SiN3, (Ph4P)2[Be2Br6] / CH2Br2, 2 days C [64] [(BeNH3)4(NH2)6]Cl2 (113) BeCl2, Be / NH3, 2 days B [65] [(BeNH3)4(NH2)6]Br2 (114) BeBr2, Be / NH3, 2 days B [65] [(BeNH3)4(NH2)6]I2 (115) NH4I, Be / NH3, 29 days B [65] [(BeNH3)4(NH2)6](CN)2 (116) Me3SiCN, Be / NH3, 2 days B [65] [(BeNH3)4(NH2)6](SCN)2 (117) NH4SCN, Be / NH3, 4 days B [65] [(BeNH3)4(NH2)6](N3)2 (118) Me3SiN3, Be / NH3, 4 days B [65]…”

“…[P4(NMe)6] (131), Me3NO / C6H6, 12 h P [90,91] [Pn(SP)4-n(NMe [P4(NMe)6] (131), Me3SiN3 / toluene, 100 °C, 12 weeks P [95] [(PNPPh3)4(NMe)6] ( 149)…”

Three-Dimensional Synthons for Cage-Dense Inorganic Polymers and Materials

“…This is because the N lone pair orbitals in the cage are permanently twisted away from the P atoms by the inability of the P–N or N–N bonds to freely rotate within the cage constraint, preventing N → P hyperconjugation. − Thus, despite being lone-pair rich (10 lone pairs in 1R , 8 lone pairs in 2R ), the geometry of these cages renders their P­(III) centers much weaker donors than in the unconstrained derivative P­(NMe 2 ) 3 . Nevertheless, it is possible to oxidize derivaties of 1R and 2R with Me 3 NO, elemental sulfur, halogens, and azides, to access the corresponding phosphine oxides, sulfides, halides, and imides, respectively. − …”