A Transient Vinylphosphinidene via a Phosphirene–Phosphinidene Rearrangement

Abstract

A room-temperature-stable crystalline 2H-phosphirene (1) was prepared by treatment of an electrophilic diamidocarbene with tert-butylphosphaalkyne. Compound 1 is shown to react as a vinylphosphinidene generated via phosphirene-phosphinidene rearrangement. Thermolysis is shown to affect C-N bond scission while reactions with CClO or (tht)AuCl afford formal oxidation of the phosphindene center and the phosphinidene-insertion into an aromatic C-C bond of a mesityl group, respectively. The latter reaction is the first example of a phosphorus analog of the Büchner ring expansion reaction.

Transition‐Metal‐Like Reversible Cycloadditions of [tBuSP‐W(CO)5] with Alkenes and Alkynes

“…The tert ‐butylthiophosphinidene complex [ t BuSP‐W(CO) 5 ] readily underwent Kukhtin–Ramirez addition with phenanthrene‐9,10‐dione to give 9 in 70 % yield, which in good agreement with the major contribution of phosphorus lone pair in the HOMO orbital (Scheme b). Stephan has reported the similar addition of low coordinated vinylphosphinidene with 3,4,5,6‐tetrachloro‐1,2‐benzoquinone or phenanthrene‐9,10‐dione.…”

Phosphorus Analogues of Methyl Nitrite and Nitromethane: CH3OPO and CH3PO2

“…In contrast to the isomerization between nitro compound RNO 2 and nitrite RONO, no isomerization for PhPO 2 (→PhOPO) was observed. Continuing the increasing interest in the fundamental chemistry of small low‐valent phosphorus compounds such as HPCO/HOCP, HC≡P, CH 3 OP/CH 3 PO, R−P=S, Me 2 N−P, R 2 C=CH−P, and H 2 NC(O)PH 2 /HC(O)PMe 2 , herein, we report the first synthesis of CH 3 OPO in cis and trans conformations through high‐vacuum flash pyrolysis (HVFP) of phosphoryl diazide CH 3 OP(O)(N 3 ) 2 . In addition to the conformational conversion of CH 3 OPO and its isomerization to CH 3 PO 2 , the elusive nitrene intermediate CH 3 OP(O)(N 3 )N in the decomposition of the diazide has also been observed (Scheme ).…”

Reversible, Room-Temperature C—C Bond Activation of Benzene by an Isolable Metal Complex

“…[7][8][9] Not unexpectedly, examples of metal-centred reactivity which lead to C-C bond cleavage in unstrained arenes are very rare, reflecting not only thermodynamic factors relating to aromatic stabilization, but also kinetic limitations due to the sterically protected and highly directional nature of the C-C bond. [10][11][12][13][14][15][16][17][18][19] Oxidative activation of the C-C bond in benzene is therefore known only in conjunction with transient, highly reactive species which are generated in situ (such as carbenes or triplet silylenes). [20][21][22][23] A well-known example is the Buchner ring expansion reaction, which classically involves the reaction of an unactivated arene with a carbene derived from a diazo-acetic ester by a thermal, photolytic or transition-metal catalysed protocol.…”