Reactions involving intramolecular cyclocarbonylation of diynes using Fe and Ru carbonyls to form cyclopentadienone metal tricarbonyl complexes have been well studied.  Our research investigates the analogous reaction using Mo and W carbonyl starting materials.  Herein, we report the intramolecular cyclocarbonylation of 1,7-diphenyl-1,6-heptadiyne with tetracarbonylbis(piperidine)molybdenum(0) to produce the <i>bis</i>(bicyclic cyclopentadienone) complex dicarbonyl <i>bis</i>(2,4-diphenylbicyclo[3.3.0]octa-1,4-dien-3-one)molybdenum(0).  The structure of the molybdenum complex was determined by X-ray crystallography.  Unlike the Fe complexes which coordinate to one cyclopentadienone group, Mo coordinates to two cyclopentadienone groups.  Based on the IR spectra, we believe the analogous W complex, dicarbonyl bis(7,9-diphenylbicyclo[4.3.0]nona-6,9-dien-8-one), has been formed using a similar diyne, 1,8-diphenyl-1,7-octadiene, though we are currently trying to obtain crystals suitable for X-ray crystallography.  These intramolecular cyclocarbonylation, sealed-tube reactions were done in a microwave reactor for 70 min in either an Ar or CO atmosphere.  Yield optimization with CO pressure is currently being investigated as well as other Mo and W starting materials and other diynes.

Synthesis of bis(cyclopentadienone)dicarbonyl complexes of Mo and W via cyclocarbonylation of α,ω-diynes

2019 Spring National Meeting

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