Transition-Metal-Substituted Acyl Phosphanes and Phosphaalkenes. 33.¹ Transition-Metal-Substituted Arsaalkenes. 3.² Reactivity of Metallodisilylphosphanes and -arsanes (η⁵-C₅Me₅)(CO)₂M−E(SiMe₃)₂ (M = Fe, Ru; E = P, As) toward Carbon Disulfide. Formation of Metallophosphaalkenes, Metalloarsaalkenes, and 1,3,4-Thiadiphospholes

Abstract

Reaction of (η5-C5Me5)(CO)2FeP(SiMe3)2 (4a) with carbon disulfide afforded the unstable metallophosphaalkene (η5-C5Me5)(CO)2Fe−PC[SSiMe3]2 (5a), which decomposed to the doubly metalated 1,3,4-thiadiphosphole 8a by extrusion of bis(trimethylsilyl)sulfide. The transient metallophosphaalkene 5a was intercepted as the isolable [(CO)5Cr]-adduct 6a by treatment with [(Z)-cyclooctene]Cr(CO)5. Similarly, the metallodisilylarsanes (η5-C5Me5)(CO)2M−As(SiMe3)2 (M = Fe, Ru) (11a,b) were converted to stable metalloarsaalkenes 12a,b by exposure to CS2. Pentacarbonylchromium complexes 13a,b were accessible by reaction with [(Z)-cyclooctene]Cr(CO)5. The X-ray structure analysis of 13a revealed the molecule as the first η1-arsaalkene complex.

Metal-phosphido and -phosphinidene complexes in P–E bond-forming reactions

“…This product was not isolable, but solution characterization including 31 P NMR spectroscopy supported the formulation (Scheme 22). 124 Ultimately, trapping reactions, such as coordination of the phosphaalkene phosphorus to a chromium center, gave products that could be fully characterized. Reactions that interconvert phosphaalkene and phosphinidene ligands at metal centers have recently been reviewed by Weber.…”

Heavy Allenes and Cumulenes ECE‘ and ECCE‘ (E = P, As, Si, Ge, Sn; E‘ = C, N, P, As, O, S)

“…Much less work has been performed on phosphathioketenes since only two papers report the formation of transient -PdCdS derivatives. 132,175 The reaction of the disilylphosphine ArP(SiMe 3 ) 2 with thiophosgene gives the four-membered ring derivative 133, which is assumed to be formed via phosphathioketene ArPdCdS intermediate 178 which dimerizes in a unsymmetrical [2 + 2]-cycloaddition 132 (eq 58). As stated previously, 133 is (by photolysis) a precursor of the corresponding diphosphaallene ArPd CdPAr 132 (eq 42).…”

η1-Ligation versus Pnictogen−Carbon Double Bond Cleavage: The Contrasting Behavior of Phospha- and Arsaalkenes [Tp*(CO)2M⋮C−EC(NMe2)2] [E = P, As; M = Mo, W; Tp* = HB(3,5-Me2pz)3] toward [Au(CO)Cl]

“…Carbon disulfide was inserted into the pnictogen−silicon bonds of metalloarsane [Cp*(CO) 2 Fe−As(SiMe 3 ) 2 ] to yield the stable ferrioarsaalkene VII . The corresponding ferriophosphaalkene, however, readily extruded (Me 3 Si) 2 S, and the resulting species dimerized to give heterocycle VIII 6 (Scheme ).…”