Synthesis and crystal structure of a molybdenum carbonyl complex, Mo(CO)4[cyclo(Ph6P3As3)], with scrambled phosphorus/arsenic identities obtained from a perfectly alternating phosphorus-arsenic heterocycle, 1,3,5-tris(phenylphospha)-2,4,6-tris(phenylarsa)cyclohexane, [cyclo(Ph6P3As3)]
✍ Scribed by Arnold L. Rheingold; Frederick P. Arnold
- Publisher
- Elsevier Science
- Year
- 1992
- Tongue
- English
- Weight
- 528 KB
- Volume
- 198-200
- Category
- Article
- ISSN
- 0020-1693
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✦ Synopsis
1,3,5-Tris(phenylphospha)-2,4,6-tris(phenylarsa)cyclohexane, cyclo(Ph.&,PB), whose perfectly alternating pnictogen structure was determined by the absence of direct P-P coupling in NMR spectra, reacts with Mo(CO), at 80 "C to form a complex, Mo(CO),[c-(Ph&,P,)], containing completely scrambled phenylpnictidene units. The structure of the complex has been crystallographically determined: monoclinic, P&/n, a = 11.756(3), b = 22.691(g), c = 14.777 A, /3 = 99.89(2)", V= 3883.5(22) A3, 2 = 4, RF= 5.66%. The original chair conformation of the heterocycle is converted to a twist-boat form in the product, but the presence of concentrated phosphorus character in the 1 and 4 positions coordinated to MO indicates that ring-opening and ring-scrambling equilibria preceded complex formation.