Reactions of acetylenes held proximate to a metal. Addition of hydrogen chloride to cis-dichlorobis(3,3,3-trifluoropropynyldiphenylphosphine)palladium(II) and -platinum(II). The x-ray structure of trans-PdCl2[Ph2PCH:C(Cl)CF3]2

Abstract

The reported boiling point for 2,4,6-trimethylpyridine is 170.5°and that for 3,5-lutidine is 171.6°. An NMR spectrum of neat 2,4,6-trimethylpyridine does not show peaks that can be unambiguously assigned to 3,5-lutidine. Use of 2,4,6-trimethylpyridine, purified by preparative gas chromatography, does not afford crystalline material. (15) The Fourier program alff was used:

The synthesis and single-crystal X-ray structures of palladium(II) and platinum(II) complexes of the difluorovinyl and 1-chloro-2-fluorovinyl-substituted phosphines, PPh2(Z-CFCFH) and PPh2(E-CClCFH)

“…In both cases these changes are consistent with steric and electronic considerations. Whilst this represents, as far as we are aware, the first structural data for a metal complex containing a CCl5 5CFH group, it is noteworthy that the Pd-P bond lengths for 4 are comparable to that reported (2.322(1) Å ) for trans-[PdCl 2 {PPh 2 (CH5 5CClCF 3 )} 2 ], the only other structurally characterised complex containing a partially fluorinated alkenyl substituent [19].…”

“…The 19 F NMR spectra of the complexes of PPh 2 (CF5 5CFH) display two multiplets, as shown in Fig. 1 for trans-[PdCl 2 {PPh 2 (CF5 5CFH)} 2 ], 1.…”

“…Infrared spectra were recorded as nujol mulls held between KBr plates on a Nicolet PC-5 FTIR spectrometer, whist Raman spectra were recorded as solid samples on a Nicolet-Nexus combined FT-IR/FT-Raman spectrometer. 19 …”

“…Furthermore, we have observed a number of The coordination chemistry of the fluorovinyl substituted phosphines PPh 2 (Z-CF5 5CFH) and PPh 2 (ECCl5 5CFH) with K 2 MX 4 (M = Pd, Pt; X = Cl, Br, and I) salts has been investigated resulting in the first reported palladium(II) and platinum(II) complexes of phosphines containing partially fluorinated vinyl groups. The complexes have been characterised by a combination of multinuclear [ 1 H, 13 C{ 1 H}, 19 F, 31 , the aggregation of fluorovinyl fragments to give a highly unusual 1:2 cis:trans-mixture of [PtCl 2 {PiPr 2 (CF5 5CF 2 )} 2 ] in the solid state and the observation of MÁ Á ÁCl secondary interactions in chlorodifluorovinyl-containing complexes [9]. For these reasons we have been interested in assessing the properties of partially fluorinated vinyl ligands of this type.…”

Homo- and hetero-dinuclear complexes of palladium and platinum containing phosphinoacetylene and/or chloride as bridging ligands

“…) 2582 ( 10) 2996 ( 10) 2735 ( 13) 2088( 1 1) 1727 ( 10) 2867( 6) 3627 (7) 3 130 (7) 1 860 ( 8) 1132 (7) 28 3 6( 9) 3294( 1 0) 4243( 13) 4803( 11) 4404( 12) 3376( 1 1) 2778( 7)…”