Science of Synthesis

Poli, R.; Smith, K. M., Science of Synthesis, (2003) 2, 300.

The dibromine oxidation of (al­kyl­idyne)bro­mo­tet­ra­car­bon­yl complexes of mo­lyb­de­num and tungsten in the presence of 1,2-di­meth­oxy­eth­ane (DME) provides a direct access to DME-stabilized (al­kyl­idyne)tri­bro­mo complexes, while the corresponding chromium systems lead to complete degradation.[‌81‌] The advantage of this procedure is the direct access to complexes with a wide variety of carbyne substituents starting from the corresponding, easily accessible Fischer-type carbyne precursor. The phen­yl derivative ‌45‌, in particular, is easily synthesized in a one-pot procedure from the precursor as shown in ‌Scheme 17‌.

‌Meeeee 88‌ Meeeeeeee ee Meeeeee-Meee Meeeeee Meeeeeeee[‌88‌,‌88‌]

Meeeeeeeeeee Meeeeeeee

Meeeeeeeeeeeeeeeeee(8,8-eeeeeeeeeeeeeee-M,M′)eeeeeeee(MM) (‌88‌, M = M):[‌88‌,‌88‌]

Me8M[M(MMMe)(MM)8] (88.88 e, 88.88 eeee) eee eeeeeeeeee eeeeeeeee ee MM8Me8 (888 eM) eeee eee eeee eee eeeeee ee −88°M. Meeeee eee­eeee (8.88 eM, 88.8 eeee) eee eeeeeeeee ee MM8Me8 (88 eM) eee eeeeee ee −88°M, eeee eeeeeee eeeee eeeeeee e M8 eeeeee ee eee eeee eeee. Meee eeee eee eeee ee eeee ee −88°M eee 88 eee, eeee eeeeee ee ee eee eeee eeee eeeee e eeeeee eeeeee eeeee eeeeeeeee. Me eee eeeeeeeeeee eeeeeeee ee −88°M; eeee eeee eeee eee eeeeeeee eeeeeee e eee-eee eeeeeeee eeee, eeeeee e 8-ee eeeee ee eee eeeeeeeee ee ee, eeee e eeeeee (−88°M) eeeeeeeee eeeee (888-eM Meeeeee). Me eee eeee ee [MMe(≡MMe)(MM)8] ee −88°M eee eeeee MMM (88 eM). M eeeeeee eeeeeeee 8.8 M eeee ee Me8 ee MM8Me8 (88 eM) eeee ee eeeeeeeeee eeeeeeee ee MM8Me8 (88 eM) eee eeeeee ee −88°M eee eeeee (eeeeee) eeeeeee e eeeeee M8 eeeeee ee eeeeeee ee eeeeeeee. Mee eeeee eeeeee eee eeeeeee eeee eeee eeeeee. Mee eeeeeee eeee eee eeeeeee ee eeee ee ee eeeee eeeeee; eeee eee eee eeeeeee eeeeee eee eeeeeee eeee. Mee eeeeeee eee eeeeeee ee eeeee eee eee eeee eeeee eeee eeeee eee eeeeee eeee eee­eeee (88 eM). Mee eeeee eee eeee eeeeeeeee ee MM8Me8 (88 eM) eee eeeeeeee. Mee eeeeee eee eeeeeee ee 88 eM eee eee­eeee (888 eM) eee eeeee eeeeeeeee ee eeeeeeeeeee eee eeeeeee ee e eeeee-eeeee eeeee. Meee eeeeeeeeeeeee eeeeeee eee eeeeeeee eeeee eee eeeeeee ee MM8Me8 eee eeeeeee eeeee. Mee eeeee eeeeeee eee e eeee eeeee eeeeeeeeeeeeeeee eeeeee; eeeee: 88.88 e (88%); 88M{8M} MMM (eeeeeee-e8, δ): 888.8 (M≡MMe).

References