Halide abstraction from vanadium trichloride by zinc chloride. Crystal structure of vanadium trichloride.zinc chloride.4 tetrahydrofuran.2 water

Synthesis and reactivity of a heterometallic carbon dioxide complex

“…Another example of electrophile-promoted reduction of carbon dioxide comes from the group of Bianchini.16 Interestingly, this group has found that the complex HCo(np3) (15) Other examples where alkali-metal cations play a prominent role in C02 transformation chemistry include Darensbourg's studies17 •18 of alkali metal ion promoted C02 insertions and Floriani's K+stabilized Co/C02 complex. 20 The spectral changes we observe upon addition of NaBPh4 and ZnBr2 are consistent with a Lewis acid-base interaction between the C02 oxygens and added electrophiles, E (eq 2). Indeed, the X-ray study does reveal that added ZnBr2 coordinates to the C02 moiety in I forming a µ4, 3 coordination mode previously unobserved for C02.…”

Bimetallic halides. Crystal structure of and ethylene polymerization by vanadium(II) chloride-zinc chloride-tetrahydrofuran (VCl2.ZnCl2.4THF)

“…In addition to such a trans effect (or coupled to it) is the diminshed oxygen pyramidality for the shorter V-O bonds in (THF)4VCl2ZnCl2, which we have suggested earlier may be indicative of bonding of the ether to the metal with more than one lone pair. 7 The arrangement of the two mutually cis THF rings seems to be consistent with this idea; one is essentially coplanar with the cis-C12V02 plane and the other perpendicular. This suggests that the oxygen lone pairs not involved in direct M-0 bonding may be interacting with two different d orbitals in a ir-bonding manner.…”

“…Suitable crystals of VCl2-ZnCl2-4THF were grown by dissolving a sample in hot THF followed by slow cooling. A crystal of irregular habit was mounted and characterized by using techniques already reported.11 Characteristics of the crystal, data collection -585 (7) 11 746 (4) -2024 (7) 9 661 (4)…”

Reactions of hydride with tungsten complexes containing organosulfur ligands: synthesis and characterization of (.mu.-hydrido)bis(.mu.-dimethyl sulfide)ditungsten(III) species

“…Very recently this hypothesis has received significant support from the work of Angelici et al, 7 who demonstrated that -bonded thiophene will react with nucleophiles, and in particular with hydride, which can be followed by protonation to produce 2,3dihydrothiophene. For this mechanism to be relevant to the catalytic hydrodesulfurization of thiophene, both hydridic and protonic hydrogen would be needed on a catalytic surface.…”