Electrophilic addition to cyanide ligands in tungsten(II) four-electron-donor alkyne complexes
- Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry
Extended reflux of Tp{prime}(CO)(I)W(RC{triple_bond}CR{prime}) (Tp{prime} = hydridotris(3,5-dimethylpyrazolyl)borate) complexes in ethyl acetate in the presence of silver cyanide produces Tp{prime}(CO)(CN)W(RC{triple_bond}CR{prime}) complexes in moderate to high yields. A single-crystal X-ray structure of Tp{prime}(CO)(CN)W(PhC{triple_bond}CMe) shows that the alkyne is aligned parallel to the M{single_bond}CO axis. Electrophilic attack at the nitrogen of the cyanide ligand with methyl triflate or triflic acid yields cationic isocyanide complexes, whereas attack with HBF{sub 4} results in neutral BF{sub 3} adduct complexes. Coordination of the Tp{prime}(CO)(PhC{triple_bond}CMe)W{sup +} fragment to the cyanide nitrogen of Tp{prime}(CO)(CN)W(HC{triple_bond}CBu{sup n}) to form a CN-bridged dinuclear complex has been achieved. Variable-temperature {sup 1}H NMR measurements reflect acetylene rotation barriers in the Tp{prime}(CO)(L)W(HC{triple_bond}CH){sup n+} series (L = CO, CNH, CNMe {l_brace}n = 1{r_brace}; CN{sup {minus}}, CNBF{sub 3}{sup {minus}} {l_brace}n = 0{r_brace}) and, thus, quantify {pi}-effects for the cyanide and isocyanide ligands with respect to steric considerations. Extended Hueckel molecular orbital calculations were carried out on a series of model complexes, [H{sub 3}(CO)(L)W(HC{triple_bond}CH)]{sup n{minus}} (L = CO, CNH {l_brace}n = 1{r_brace}; CN{sup {minus}}, H{sup {minus}} {l_brace}n = 2{r_brace}) to augment the experimental data.
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- DOE Contract Number:
- FG02-96ER14608
- OSTI ID:
- 655375
- Journal Information:
- Organometallics, Journal Name: Organometallics Journal Issue: 17 Vol. 17; ISSN ORGND7; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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