Preparation of [(η5-MeC5H4)Mn(CO)(NO)(DMPP)]PF6, DMPP = 1-Phenyl-3,4-Dimethylphosphole, and its Intramolecular [4+2] Diels-Alder Cycloaddition Reaction with Ph2PCH=CH2
- 1 March 1999
- journal article
- research article
- Published by Taylor & Francis in Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry
- Vol. 29 (3) , 395-406
- https://doi.org/10.1080/00945719909349459
Abstract
(η5-MeC5H4)Mn(CO)3 reacts with NaNO2, HCI and KPF6 to form [(η5-MeC5H4)Mn(NO)(CO)2]PF6(1). Compound (1) reacts with 1-phenyl-3,4-dimethylphosphole (DMPP) to form [(η5-MeC5H4)Mn(NO)(CO)(DMPP)]PF6(2). Compound (2) reacts with Ph2PCH=CH2 (DPVP) to form [(η5-MeC5H4)Mn(NO) (DMPP)(DPVP)]PF6(3), which undergoes an intramolecular [4+2] Diels-Alder cycloaddition reaction at 50°C to form [(η5-MeC5H4)Mn(NO)(2-diphenyl-phosphino)-5,6-dimethyl-7-phenyl-7-phosphabicyclo[2. 2. 1]hept-5-ene)]PF6(4a,b). The new complexes were characterized by elemental analyses, physical properties, infrared spectroscopy, and 1H, 13C{1H}and “P(1H) NMR spectroscopy. The structures of (2) and (4a) were confirmed by X-ray crystallography. They crystallize in the Pna21 and P21/n space groups, respectively, in unit cells of the following dimensions: (2): a = 19. 333(3)Å, b = 11. 011(1)Å, c = 10. 562(2)Å, α = β = γ = 90°, p(calc) = 1. 552 g er−3, Z = 4. (4a): a = 10. 932(2)Å, b = 19. 220(2)Å, c = 16. 957(2)Å, β = 104. 62(1)°, p(calc) = 1. 367 g cm−3, Z = 4. Refinements converged to R(F) = 0. 0562 and 0. 0752 for 2358 and 4504 independent observed (I ≥ 20° (I)) reflections, respectively.Keywords
This publication has 12 references indexed in Scilit:
- Intramolecular [4+2] Diels−Alder Cycloaddition of a 2H-Phosphole to Coordinated Unsaturated Phosphines, Phospholes, and an ArsineJournal of the American Chemical Society, 1997
- Synthesis and absolute stereochemistry of an organo-palladium complex containing a P-chiral diphosphine ligandJournal of Organometallic Chemistry, 1997
- Iron-promoted intramolecular [4 + 2] Diels-Alder cycloadditions of 1-phenyl-3,4-dimethylphosphole with selected dienophilesOrganometallics, 1992
- Stereoisomerism and local chiralityJournal of the American Chemical Society, 1984
- An Improved One-Pot Synthesis of PhospholesSynthesis, 1981
- Optisch aktive übergangsmetall-komplexe: XXXIII. Substituenteneinfluss auf die racemisierungs geschwindigkeit von (+)579und(−)579−C5H5MN(COC6H5)(NO)P(pC6H4Y)3Journal of Organometallic Chemistry, 1976
- Complexes of (methylsulfinyl)methyllithium and -sodium, with Lewis basesJournal of Organometallic Chemistry, 1970
- Reactions of the dicarbonyl substituted cyclopentadienyl nitrosyl manganese complex cation [(π-C5H4)Mn(NO)(CO)2]+with some nitrogen and phosphorus donor ligandsJ. Chem. Soc. A, 1970
- Über nitrosyl-metall-komplexe X. Substitutionsreaktionen an [C5H5Mn(CO)2NO]+[PF6]− mit neutralen donorligandenJournal of Organometallic Chemistry, 1969
- Organometallic Chemistry of the Transition Metals. VII. Cyclopentadienylmetal Nitrosyl Derivatives of Chromium and Manganese with Bridging Nitrosyl GroupsInorganic Chemistry, 1964