c ~s -R ~C I ( C O ) ~P ~~P ( C H ~) ~P ( O ) P ~~, the only species observed during catalysis, formed from cis-hhCI(CO)Ph2P(CH2P(~)Ph2 and CO, is the sole active species observed during catalytic studies and results in the carbonylation of methanol with catal st turnover frequencies approaching 400 h-1 at 80°C and 50 psig CO; the crystal structure of the analogue cis-hCI(CO)Ph2PCH2P(0)Ph2 is reported.
Treatment of the lithium derivative of c/y-4,6-dimethyl-l,3-dithiane (1) with DC1 gives nearly exclusively (over 99%) the equatorial 2-deuterio compound (la), treatment with methyl iodide gives exclusively the equatorial methyl compound (r-2,c/j-6,cii-4-trimethyl-l,3-dithiane, 2), and treatment with carbonyl compounds (formaldehyde, acetone, and pivalic aldehyde) gives the equatorial carbinols (4) in at least 99.8% isomeric purity.
Triphenylphosphine is converted into propyldiphenylphosphine rapidly during rhodium-catalyzed propylene hydrogenation and more slowly during low-pressure propylene hydroformylation. The pathway for this conversion involves the reversible oxidative addition of a phenyl-phosphorus bond of triphenylphosphine to rhodium, followed by the reductive elimination of propyldiphenylphosphine from a (diphenylphosphido)propylrhodium intermediate. The effects of reaction variables on this triphenylphosphine reaction have been studied, and a mechanism is proposed.
CH3CN)2MoBr(CO)2(7)3-C8H13)], 81923-03-7; (+)-[NMCpMo-(NO)(CO)(i/3-C8H13)]BF4, 89689-90-7; (+)-[NMCpMo(NO)-(CO)(i73-C8H13)]PF6, 89772-14-5; (-)-[NMCpMo(NO)(CO)(7,3-C8H13)]BF4, 89771-47-1; (+)-NMCpMo(NO)(Br)(7,3-C8H13), 89689-91-8; (-)-NMCpMo(NO)(Br)(r)3-C8H13), 89771-48-2; (-)D-NMCpMo(NO) (CO) (7j2-C8H13OH), 89689-92-9; (-)D-NMCpMo-(NO)(CO)(tj2-C8H13D), 89689-93-0; Mo(CO)6,13939-06-5; NOBF4, 14635-75-7; NaBr, 7647-15-6; 3-bromocyclooctene, 7422-06-2;(-)-cycloocten-3-ol, 62210-83-7; (-)-3-deuteriocyclooctene, 89689-94-1; silver hexafluorophosphate, 26042-63-7; neomenthylcyclopentadiene, 89689-88-3. Supplementary Material Available: Tables of anisotropic temperature factors, calculated hydrogen atom positions, and structure factors for both crystal modifications of the bromide structure and tables of crystal data, positional parameters, bond lengths, and bond angles for the P2i modification (26 pages). Ordering information is given on any current masthead page.
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