Reactions of the persistent phosphinyl radical •P[CH(SiMe_{3})_{2}]_{2} with elemental chalcogens

Abstract

The persistent phosphinyl radical •P[CH(SiMe3)2]2 reacts readily with elemental sulfur, selenium or tellurium to afford the chalcogen-bridged derivatives of formula R2P-X-PR2 [R = (Me3Si)2CH; X = S, Se, Te], each of which was characterized by single-crystal X-ray diffraction.

Preparation of a Diphosphine with Persistent Phosphinyl Radical Character in Solution: Characterization, Reactivity with O2, S8, Se, Te, and P4, and Electronic Structure Calculations

“…Interestingly, we found that the two halves of the diphosphine are present in the solid state, and through careful analysis of the disorder present we found that the sulfide and disulfide cocrystallize in an 87:13 ratio roughly matching the ratio of products seen in the 31 P NMR spectrum (Figure ). This product is similar to that recently reported by Cowley et al in the reaction of (Me 3 Si) 2 CH) 2 P–P(CH(SiMe 3 ) 2 ) 2 with elemental sulfur . However, in that case, the authors report that all of their reaction attempts resulted in intractable mixtures, and in one case were only able to isolate one single crystal for analysis.…”

Condensation Reactions of Chlorophosphanes with Chalcogenides

“…The P–Ch bond lengths (Table ) are comparable to those reported in the literature (cf. 2 S (N( i Pr) 2 ) , 2 Te (N( i Pr) 2 ) , 2 Ch (CH(SiMe 3 ) 2 ) (see Table ), and 2 Te ((CH 2 ) 2 (NDipp) 2 ) (P–Te 2.584(7) Å, 2.587(8) Å)). As expected, in all derivatives, the P–Ch bond length increases with higher atomic number of the Ch atom.…”

“…Phosphane (CF 3 ) 2 PCl can be converted to the corresponding diphosphanylsulfanes 2 S (CF 3 ) by the reaction with either H 2 S or Ag 2 S as sulfide sources under harsh conditions and after long reaction times (100 °C, 19 days) . Derivatives of diphosphanylselanes- and tellanes ( 2 Ch (R) ; R = t Bu, N­( i Pr) 2 ; Ch = Se, Te) are prepared in a similar manner to the sulfur derivative 2 S (N( i Pr) 2 ) or via chalcogenation of persistent phosphanyl radicals. , …”

“…10 Derivatives of diphosphanylselanes-and tellanes 11 (2 Ch (R) ; R = tBu, N(iPr) 2 ; Ch = Se, Te) are prepared in a similar manner to the sulfur derivative 2 S (N(iPr) 2 )12 or via chalcogenation of persistent phosphanyl radicals. 13,14 In this context, we present a versatile and high-yielding protocol for the selective synthesis of 1 Ch (R) and 2 Ch (R) via a facile condensation reaction of monochlorophosphanes (R 2 PCl) with sodium chalcogenides (Na 2 Ch, Ch = S, Se, Te). The In the reactions of volatile alkyl-substituted R 2 PCl (R = Me, Et) and (Me 3 Si) 2 Ch, isolation of the analytically pure products involves simple removal of all volatiles in vacuo.…”

The Reactivity of Germanium Phosphanides with Chalcogens

“…38 The Ge−Te bond length of 2.6516(6) Å is longer that that reported for βdiketiminatogermanium(IV) tellurides (2.415−2.424 Å), and the Te−P bond of 2.4705 (13) Å is between that of a single bond of [Te(PSiMe 3 ) 2 ] (2.505−2.552 Å) and double bond of [TePCy 3 ] (2.3632(7) Å). 26,37,39 The Ge−Te−P bond angle of 88.12(3)°is significantly more acute than the Ge−Se−P bond angle of 2-Cy-Se (94.07(3)°). Complex 2-Cy-Te is not only a rare example of a phosphinochalcogenoite ligand (R 2 PE¯) ligand, 21,40 but it is the first example of a dialkylphosphinotelluroite ligand.…”