dc.contributor.author | Lucas, NT | |
dc.contributor.author | Humphrey, MG | |
dc.contributor.author | Healy, PC | |
dc.contributor.author | Williams, ML | |
dc.date.accessioned | 2017-05-03T13:38:06Z | |
dc.date.available | 2017-05-03T13:38:06Z | |
dc.date.issued | 1997 | |
dc.date.modified | 2009-08-25T03:45:11Z | |
dc.identifier.issn | 0022-328X | |
dc.identifier.doi | 10.1016/S0022-328X(97)00346-X | |
dc.identifier.uri | http://hdl.handle.net/10072/15591 | |
dc.description.abstract | Reactions of Cp2Mo2Ir2(CO)10 (1) with stoichiometric amounts of phosphines afforded the substitution products Cp2Mo2Ir2(CO)10-xLx (L = PPh3, x = 1 (5), 2 (6); L = PMe3, x = 1 (7), 2 (8)), in fair to excellent yields (36-78%), shown by low temperature 31P NMR to consist of mixtures of interconverting isomers. An X-ray structural study of Cp2Mo2Ir2(孃O)3(CO)6(PMe3) (7a), one isomer of 7, revealed that the PMe3 ligand occupies the electronically-preferred axial site (with respect to the plane of the bridging carbonyls). Geometries of all other isomers of 5-8 have been postulated from a combination of NMR data and results from the analogous Cp2W2Ir2(CO)10 system. Reactions of 1 with a range of alkynes afforded Cp2Mo2Ir2(崭?2-RC2R')(CO)8 (R = R' = Ph (9), H (14); R = H, R' = Ph (10), 4-C6H4NO2 (11), 4,4'-C6H4Ctriple bond; length as m-dashCC6H4NO2 (12), CH2Br (13)) in fair to good yields (34-80%). An X-ray structural study of 10 revealed that the alkynes have formally inserted into the Mo-Mo bond of 1, to afford clusters with a pseudooctahedral core geometry. Qualitative analysis of reaction rates for the syntheses of 9-14 revealed the trends acetylene> terminal alkyne> internal alkyne and 4-nitrophenylacetylene> phenylacetylene, assigned to a combination of electronic and steric effects. | |
dc.description.peerreviewed | Yes | |
dc.description.publicationstatus | Yes | |
dc.language | English | |
dc.language.iso | eng | |
dc.publisher | Elsevier Science | |
dc.publisher.place | Switzerland | |
dc.publisher.uri | http://www.sciencedirect.com/science/journal/0022328X | |
dc.relation.ispartofpagefrom | 519 | |
dc.relation.ispartofpageto | 530 | |
dc.relation.ispartofjournal | Journal of Organometallic Chemistry | |
dc.relation.ispartofvolume | 545-546 | |
dc.subject.fieldofresearch | Inorganic chemistry | |
dc.subject.fieldofresearch | Organic chemistry | |
dc.subject.fieldofresearch | Other chemical sciences | |
dc.subject.fieldofresearchcode | 3402 | |
dc.subject.fieldofresearchcode | 3405 | |
dc.subject.fieldofresearchcode | 3499 | |
dc.title | Mixed-metal Cluster Chemistry VII: Some Phosphine and Alkyne Chemistry of Cp2Mo2Ir2(CO)10; X-ray Crystal Structures of Cp2Mo2Ir2(u-CO)3(CO)6(PMe3) and Cp2Mo2Ir2(u4-n2HC2Ph)(u-CO)4(CO)4 | |
dc.type | Journal article | |
dc.type.description | C1 - Articles | |
dc.type.code | C - Journal Articles | |
gro.rights.copyright | © 1997 Elsevier. Please refer to the journal's website for access to the definitive, published version. | |
gro.date.issued | 1997 | |
gro.hasfulltext | No Full Text | |
gro.griffith.author | Healy, Peter C. | |