Synthesis of Novel O,P,C-Cage Complexes via Thermal C−O Ring Opening of an Oxaphosphirane W(CO)₅ Complex

Abstract

A facile and highly stereoselectiVe synthesis of noVel O,P,C-cage complexes Via thermal C-O ring opening of an oxaphosphirane W(CO) 5 complex is described. All compounds were unambiguously characterized by elemental analysis, multinuclear NMR, IR, MS, and single-crystal X-ray diffraction studies.

First synthesis of chloroformylphosphane complexes

“…Dichlorophosphane complexes 1a-c [8][9][10] which were reacted in situ with phosgene at -105 °C to give P-chloro chloroformylphosphane complexes 3a-c and chlorophosphanes 1a-c and 4a-c in different ratio, depending on the reaction conditions applied (Scheme 1). The formation and stability of chloroformylphosphane complexes 3a-c was found to be largely dependent on the nature of the substituents at phosphorus, the amounts of phosgene solution employed, and the temperature regime.…”

Unprecedented Ring–Ring Interconversion of N,P,C‐Cage Ligands

“…Since tetraphosphacubane1 was obtained by phospha‐alkyne cyclo‐oligomerisation reactions in the late 1980s, the chemistry of P,C‐cage compounds has expanded significantly. Despite this, few synthetic methods have been devised to prepare P,C‐cage derivatives, including those incorporating further heteroatoms such as oxygen,2 nitrogen3 or phosphorus,4 and most of these were obtained only within the coordination sphere of a transition metal and/or by using P ‐pentamethylcyclopentadienyl (Cp*)‐substituted reactive species such as terminal5 and bridging6 phosphinidene complexes; recently, access to ionic cages and/or polycycles was also reported 7…”

Synthesis and structure of {{amino(triorganosilyl)carbene}pentacarbonyltungsten(0)} complexes and attempted synthesis of {[2-bis(trimethylsilyl)methyl-3-triorganosilyl-2H-azaphosphirene-κP]pentacarbonyltungsten(0)}

“…One of the current challenges in the chemistry of 2H-azaphosphirene complexes [1,2] is C-and/or P-functional derivatives that would allow to exploit the chemistry in new directions. Up to now, only two examples of C-functional compounds were isolated, both containing N-bonded amino groups, i.e., dimethylamino [3] or piperidino.…”

“…[4] This apparent lack motivated us to start new investigations aiming at expanding this chemistry by the introduction of other heteroatoms bound to the 2H-azaphosphirene carbon and as triorganosilyl groups have a great versatility in protection group chemistry [5] including easy replacement by other groups, we decided to work first on these derivatives. Although three different routes were established over the years, namely the aminocarbene condensation/rearrangement cascade (1), [1] the thermal phosphinidene complex group transfer reaction (2) [4] and, more recently, the reaction of Li/X phosphinidenoid complexes at low temperature (3), [3] we turned to the still most versatile route (1) to generate 2H-azaphosphirene complexes. Here, an aminocarbene complex I reacts with P-chloro alkylidenephosphane II in the presence of triethylamine to give 2H-azaphosphirene complexes VI via the reactive intermediates IIIeV (Scheme 1).…”