ChemInform Abstract: Synthesis and Structure of Bis(bis(diisopropylamino)phosphino) chalcogenides.

Abstract

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

“…In turn, these P-X-P angles are similar to those reported for (i-Pr 2 N) 2 P-S-P(N-i-Pr 2 ) (100.1(1) • ) and (i-Pr 2 N) 2 P-Te-P(N-i-Pr 2 ) (94.4(1) • ) by Niecke et al [13]. It is also interesting to note the structural consequences of inserting a chalcogen atom into the P-P bond of bulky diphosphine 2.…”

Organophosphorus–Tellurium Chemistry: From Fundamentals to Applications

“…( Figure 5b) and 19b confirmed the acyclic arrangement with long P-Te bonds of 2.56 Å (19a) 63 and 2.59 Å (19b) 64 and narrow P-Te-P bond angles of 94.5° for 19a, cf. 100° for the sulfur analog, 63 and 83.0 (2) .…”

“…63 Very recently, a bulky analog (RR′N) 2 P-Te-P(NRR′) 2 (19b, R = Dipp, R′ = -CH 2 -) was isolated as colorless crystals in 82% yield from a similar, but more rapid (16 h in THF), tellurium-insertion process. 64,65 Crystal structure determinations of 19a…”

“…100° for the sulfur analog, 63 and 83.0 (2) . 66 The 1 J( 31 P, 125 Te) values for 18a and 18c are reduced substantially (by 127 and 177 Hz, respectively) upon complexation to chromium ( …”

The Reactivity of Germanium Phosphanides with Chalcogens

“…As with the germanium(IV) selenide 5-Cy-Se, the Ge−N and Ge−P bonds 3-Cy-S are shorter than those in the germanium(II) dicyclohexylphosphanide 1-Cy precursor (ΔGe−N(ave) = 0.09 Å and ΔGe−P = 0.14 Å), with the Ge−S bond distance of 2.0954(8) Å slightly longer than that of 5-Cy-S. Although we were unable to assign the resonance at δ P 97.7 ppm in the 32 and the 125 Te NMR spectrum displays a doublet at −296.8 ppm (|J PTe | = 406 Hz). This reactivity is different from oxidative-addition chemistry generally observed between tellurium and germanium(II) complexes, 31,33−37 including other β-diketiminato germanium complexes 37 as well as aminotroponiminato germanium complexes.…”