Synthesis, redox properties, EPR and ENDOR spectroscopy of the 17-electron cycloheptatrienylmolybdenum complexes [MoX(Ph2PCH2CH2PPh2)(η-C7H7)]z+ (z = 1, X = I, Br, Cl, F, NCO, NCS, CN, 13CN, Me, CCPh; z = 2, X = NCMe, CNMe, 13CNMe, oxacyclopentylidene)

Aston, Georgina M.; Badriya, Samer; Farley, Rebecca; Grime, Richard W.; Ledger, Sarah J.; Mabbs, Frank E.; McInnes, Eric J. L.; Morris, Hugh W.; Ricalton, Allen; Rowlands, Christopher C.; Wagner, Kirsten; Whiteley, Mark W.

doi:10.1039/a907205e

Cited by 28 publications

(13 citation statements)

References 23 publications

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“…i Estimated from the data quoted in [79]. j Estimated from the data quoted in [56], concerning the carbene complex with the {Mo(g 7 -C 7 H 7 )(dppe)} + metal center. k Quasi-reversible oxidation wave.…”

Section: Carbenesmentioning

confidence: 99%

“…p Proposed [37] on the basis of S M and I M values obtained from a restricted number of data points (see Table 4). q Original E value from [56].…”

Section: Carbenesmentioning

confidence: 99%

“…Most of them have been obtained in this work from the quoted oxidation potential of their complexes commonly with the {M(CO) 5 } (M = Cr, Mo, W) metal center [5,30,[35][36][37][77][78][79][80][81], but, in the case of the cyclic oxocarbene CCH 2 CH 2 CH 2 O, the available complex has the halfsandwich cycloheptatrienyl {Mo(g 7 -C 7 H 7 )(dppe)} + center [55,56]. P L has been calculated by using either its definition expression (Eq.…”

Section: Carbenesmentioning

confidence: 99%

“…Other indirect methods for the estimate of E s , b and/or P L have been used for certain types of 18-electron complexes, such as [M s LL 0 ] [31][32][33] and [M s L n ] [5,13] Values of the P L and E L parameters for selected ligands are shown in Table 2 [14,18,21,27,[29][30][31][32][33][34]36,[41][42][43][44][45][46][47][48][49][50][51][52][53][54], whereas E s , b and S M , I M parameters are listed in Tables 3 [5,14,27,30,[32][33][34][35]42,[44][45][46][47]49,55,56] and 4 [18,19,…”

Section: Introductionmentioning

confidence: 99%

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Electron-donor/acceptor properties of carbynes, carbenes, vinylidenes, allenylidenes and alkynyls as measured by electrochemical ligand parameters

Pombeiro¹

2005

Journal of Organometallic Chemistry

116

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Section: Carbenesmentioning

confidence: 99%

“…p Proposed [37] on the basis of S M and I M values obtained from a restricted number of data points (see Table 4). q Original E value from [56].…”

Section: Carbenesmentioning

confidence: 99%

Section: Carbenesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Electron-donor/acceptor properties of carbynes, carbenes, vinylidenes, allenylidenes and alkynyls as measured by electrochemical ligand parameters

Pombeiro¹

2005

Journal of Organometallic Chemistry

116

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“…These species are invoked as intermediates in many syntheses; some of them, for example, have been proposed as catalysts for olefin metathetical polymerization [5], while metal-centred radicals derived from carbonyl complexes, are frequently used for their exceptional substitutional lability [6][7][8]. Intense efforts have been devoted to describe the electronic structure of 17-electron Mo complexes [9][10][11]. Since these compounds can often be produced by electrochemical oxidation of 18-electron species, liquid solution electron paramagnetic resonance (EPR) spectra have been used to provide information about their spin delocalization; however, under these conditions only the isotropic hyperfine constants and the average values of the g-tensors can be determined.…”

Section: Introductionmentioning

confidence: 99%

Single-crystal EPR study and DFT structure of the [Mo(CO)5PPh3]+· radical cation

Sidorenkova

Berclaz

Ndiaye

et al. 2009

Journal of Physics and Chemistry of Solids

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a b s t r a c tA radical species characterized by a large g-anisotropy and a clearly resolved hyperfine structure with 95/97 Mo and 31 P nuclei is formed, at 77 K, by radiolysis of a single crystal of Mo(CO) 5 PPh 3 . The corresponding EPR signals disappear irreversibly with increasing temperature and the angular dependence of the various coupling constants imply a spin delocalization of $60% and $4% on the molybdenum and the phosphorus atoms, respectively and are, a priori, consistent with the trapping of a one-electron deficient centre. The ability of DFT to predict the EPR tensors for a 17-electron Mo (I) species is verified by calculating the g-tensor and the various 14 N and 13 C coupling tensors previously reported by Hayes for [Mo(CN) 5 NO] 3À . Calculations at the B3LYP/ZORA/SOMF level of theory show that, in contrast to Mo(CO) 5 PH 3 , one-electron oxidation of Mo(CO) 5 PPh 3 causes an appreciable change in the geometry of the complex. The g-tensor and the 95/97 Mo and 31 P isotropic and anisotropic coupling constants calculated for [Mo(CO) 5 PPh 3 ] + Á confirm the trapping of this species in the irradiated crystal of Mo(CO) 5 PPh 3 ; they also show that the conformational modifications induced by the electron release are probably hindered by the nearby complexes.

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Synthesis, Stereochemistry and Molecular Structures of Chiral-at-Metal (Cycloheptatrienyl)molybdenum Complexes Containing the Diphosphane Prophos

Brunner

Klankermayer

Zabel

2002

Eur. J. Inorg. Chem.

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The synthesis of a series of 18-electron chiral-at-metal (cycloheptatrienyl)molybdenum complexes [(η 7 -C 7 H 7 )Mo(prophos)X] [prophos = (R)-1,2-bis(diphenylphosphanyl)propane; X = NCMeBF 4 , Cl, I, CN, H, Me] is reported, which consist of diastereomers differing only in the metal configuration. Diastereomer enrichments have been achieved and the configurational stability of the compounds [(η 7 -C 7 H 7 )Mo(pro-

show abstract

Synthesis, redox properties, EPR and ENDOR spectroscopy of the 17-electron cycloheptatrienylmolybdenum complexes [MoX(Ph2PCH2CH2PPh2)(η-C7H7)]z+ (z = 1, X = I, Br, Cl, F, NCO, NCS, CN, 13CN, Me, CCPh; z = 2, X = NCMe, CNMe, 13CNMe, oxacyclopentylidene)

Cited by 28 publications

References 23 publications

Electron-donor/acceptor properties of carbynes, carbenes, vinylidenes, allenylidenes and alkynyls as measured by electrochemical ligand parameters

Electron-donor/acceptor properties of carbynes, carbenes, vinylidenes, allenylidenes and alkynyls as measured by electrochemical ligand parameters

Single-crystal EPR study and DFT structure of the [Mo(CO)5PPh3]+· radical cation

Synthesis, Stereochemistry and Molecular Structures of Chiral-at-Metal (Cycloheptatrienyl)molybdenum Complexes Containing the Diphosphane Prophos

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