Contribution to the Chemistry of (ClC{PPh₃}₂)Cl, a Precursor of the Carbodiphosphorane C(PPh₃)₂

Abstract

Abstract. The salt (ClC{PPh 3 } 2 )Cl (1), formally seen as an addition compound between the carbone C(PPh 3 ) 2 2+ was also formed from the

Proton Affinities of Cationic Carbone Adducts [AC(PPh3)2]+(A=Halogen, Hydrogen, Methyl) and Unusual Electronic Structures of the Cations and Dications [AC(H)(PPh3)2]2+

“…The C−F bond length does not change markedly upon protonation but the distances of the P atoms to C(1) have experienced the typical elongation to normal single bonds, amounting to a mean value of 1.860 Å usually found in type II compounds. Shrinking of the P‐C‐P angle to about 121° proceeds upon protonation similarly as in the chlorine analog 1 Cl(H) 2+ . As a result of another run in CH 2 Cl 2 and layering with n ‐pentane, minor quality crystals of 1 F(H) Br 2 ⋅ CFBr 3 ‐S were obtained, however, with nearly identical but less precise parameters (see the Supporting Information).…”

“…Chem.E ur.J.2016, 22,8536-8546 www.chemeurj.org 1Cl(H) 2+ . [23] As ar esult of another run in CH 2 Cl 2 and layering with n-pentane, minor quality crystalso f1F(H)Br 2 ·CFBr 3 -S were obtained, however,w ith nearly identical but less precise parameters (see the Supporting Information).…”

“…For the 31 P NMR and 19 F NMR spectra, we used a Bruker AC 300 spectrometer; 13 C and 1 H spectra were run on an AC Bruker 300 spectrometer. [ClC(PPh 3 ) 2 ]Cl ( 1 Cl Cl) and [ClC(H)(PPh 3 ) 2 ]Cl 2 ( 1 Cl(H) Cl 2 ) were prepared according to literature procedures . CFBr 3 was purchased from Aldrich and stored under an argon atmosphere and dried over molecular sieves.…”

“…[ ClC(PPh 3 ) 2 ]Cl (1ClCl) and [ClC(H)(PPh 3 ) 2 ]Cl 2 (1Cl(H)Cl 2 ) were prepared according to literature procedures. [23] CFBr 3 was purchased from Aldrich and stored under an argon atmosphere and dried over molecular sieves. CCDC 1450604 (1FBr); 1450605 (1BrBr), 1450606 (1F(H)Br 2 ·HCl·C 7 H 8 ), 1450607 (1FBr-S), and 1450608 (1F(H)Br 2 ·CFBr 3 -S) contain the supplementary crystallographic data for this paper.T hese data are provided free of charge by The Cambridge Crystallographic Data Centre.…”

“…Although all type Ic ompounds possess al one electron pair with p symmetry at C(1), additional uptake of at least the smallest Lewis acid H + to give typeIIc ompounds is not commona nd, to the best of our knowledge,r estricted to the species[ AC(PPh 3 ) 2 ] + with A = H, F, Cl, and Me. [22] In earlier works, we described the protonation of 1Cl + + to produce 1Cl(H) 2 + + [23] and the structure of 1Cl + + . [24] Type II compounds with main-group Lewisa cids, A, whichh ave been structurally characterized by X-ray analysis are limited to adducts of ac arbone to two boron, [25] two sulfur, [26] andt ot wo fluorine [21] atoms.…”