Group 4 metal mono-dicarbollide piano stool complexes. Synthesis, structure, and reactivity of ({eta}{sup 5}-C{sub 2}B{sub 9}H{sub 11})M(NR{sub 2}){sub 2}(NHR{sub 2}) (M = Zr, R = Et; M = Ti, R = Me, Et)
- Univ. of Iowa, Iowa City, IA (United States)
- Northern Illinois Univ., Dekalb, IL (United States)
The amine elimination reaction of C{sub 2}B{sub 9}H{sub 13} and Zr(NEt{sub 2}){sub 4} yields the mono-dicarbollide complex ({eta}{sup 5}-C{sub 2}B{sub 9}H{sub 11})Zr(NEt{sub 2}){sub 2}(NHEt{sub 2}), (1), which has been shown to adopt a three-legged piano stool structure by X-ray crystallography. Crystal data for 1: space group P2{sub 1}/c, a = 10.704(4) A, b = 11.066(3) A, c = 20.382(8) A, {beta} = 99.20(3){degree}, V = 2383(1) A{sup 3}, Z = 4. Complex 1 undergoes facile ligand substitution by THF and 4-picoline, yielding ({eta}{sup 5}-C{sub 2}B{sub 9}H{sub 11})Zr(NEt{sub 2}){sub 2}-(THF) (2) and ({eta}{sup 5}-C{sub 2}B{sub 9}H{sub 11})Zr(NEt{sub 2}){sub 2}(4-picoline){sub 2} (3). Compound 3 exists as the four-coordinate species ({eta}{sup 5}-C{sub 2}B{sub 9}H{sub 11})Zr(NEt{sub 2}){sub 2}(4-picoline) in CH{sub 2}Cl{sub 2} solution. Complex 1 reacts selectively with 2 equiv of [NH{sub 2}ET{sub 2}]Cl, yielding ({eta}{sup 5}-C{sub 2}B{sub 9}H{sub 11})ZrCl{sub 2}(NHEt{sub 2}){sub 2} (4). Similarly, the reaction of C{sub 2}B{sub 9}H{sub 13} and Ti(NR{sub 2}){sub 4} yields ({eta}{sup 5}-C{sub 2}B{sub 9}H{sub 11})Ti(NR{sub 2}){sub 2}(NHR{sub 2}) (5, R = Me; 6, R = Et). Compounds 1-6 are potential precursors to group 4 metal ({eta}{sup 5}-C{sub 2}B{sub 9}H{sub 11})MR{sub 2}L{sub n} alkyl species. 25 refs., 3 figs., 3 tabs.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 102859
- Journal Information:
- Organometallics, Journal Name: Organometallics Journal Issue: 8 Vol. 14; ISSN ORGND7; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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