Substituted metal carbonyls. 26.1 One-step synthesis, structures, NMR, and dynamic laser-light scattering of Re2(μ-OMe)2[μ-Ph2P(CH2) nPPh2](CO)6 (n = 1-4)

Content Provider	Semantic Scholar
Author	Low, Pauline Meng Neo Yong, Y. L. Hor, Tzi Sum Andy Chan, Kam Kwong Au-Yeung, Steve Chik Fun Wen, Yuh-Sheng Liu, Ling Kang
Copyright Year	1996
Abstract	Oxidative decarbonylation of Re2(CO)10 by Me3NO in a mixture of THF and MeOH followed by addition of alkyl-chained diphosphine Ph2P(CH2)nPPh2 (PP) (n ) 1-4) gives Re2(μ-OMe)2(μ-PP)(CO)6 in 34, 29, 28, and 10% yields, respectively. This methanolytic oxidation across the Re-Re bond provides a general and one-step route for the synthesis of these dirhenium hexacarbonyl complexes with diphosphine and methoxo bridges. The molecular structure of Re2(μ-OMe)2(μ-Ph2PCH2PPh2)(CO)6 was determined by single-crystal X-ray diffraction analysis. It contains two fac-[Re(CO)3] moieties bridged by dppm and two methoxo ligands. The {Re2O2} core is significantly more planar than that in the Fe(C5H4PPh2)2 analogue. That such a dinuclear core is maintained in spite of the different steric demands of the different bridging diphosphines illustrates the great geometric tolerance of the bridging methoxo groups. The fluxionality of the dppm, dppe, and dppp complexes has been studied and compared by molecular modeling and solution 1H NMR spectroscopy. Dynamic laserlight scattering (DLS) shows that the dppe complex aggregates in CH2Cl2 to form small clusters with an average radius of ∼370 nm. The use of a combination of DLS and NMR in organometallic chemistry is unprecedented.
Starting Page	1369
Ending Page	1375
Page Count	7
File Format	PDF HTM / HTML
DOI	10.1021/om9506779
Alternate Webpage(s)	http://chiwu.chem.cuhk.edu.hk/pub/Organometallics/om96_15_1369.pdf
Alternate Webpage(s)	https://doi.org/10.1021/om9506779
Volume Number	15
Language	English
Access Restriction	Open
Content Type	Text
Resource Type	Article