Transition-metal derivatives of the functionalized cyclopentadienyl ligand. XVI. Synthesis of the bridged complexes [(μ-η5-C5H4PPh2)M(CO)2]2 (M=Cr, Mo, W). X-Ray crystal structure of the dihydride derivative [(μ-η5-C5H4PPh2)W(CO)2H]2

Brumas-Soula, Brigitte; Dahan, Françoise; Poilblanc, and Rene′

doi:10.1039/a706746a

Cited by 7 publications

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“…The relevant angles are summarized in Table 1. Similar structural motifs have been observed for other homo‐dinuclear metal complexes in the absence of metal–metal bonds, for example, [{(μ‐η 5 ‐C 5 H 4 PR 2 )Rh(CO)} 2 ] (R=Ph, Me),16 [{(μ‐η 5 ‐C 5 H 4 PPh 2 )W(CO) 2 H} 2 ],17 [{(μ‐η 5 ‐C 5 H 4 PPh 2 )NiX} 2 ] (X=Br, CH 3 ),18 [{(μ‐η 5 ‐C 5 H 4 PPh 2 )PtPh} 2 ], [{(μ‐η 5 ‐C 5 H 4 PPh 2 )PdMe} 2 ],19 and [{(μ‐η 5 ‐C 5 H 4 PPh 2 )Ag(PR 3 )} 2 ] (R=Ph, Et) 20. Phosphane coordination leads to a marked deviation from the coplanar orientation of the Cp and Cht rings that is observed for 2 and 3 ;5 the angles subtended at the metal center by the ring centroids are 145.2/145.9° ( 10 a ) and 145.9° ( 11 a ).…”

Section: Resultssupporting

confidence: 71%

“…[{(m-h 5 -C 5 H 4 PPh 2 )W(CO) 2 H} 2 ], [17] [{(m-h 5 -C 5 H 4 PPh 2 )NiX} 2 ] (X = Br, CH 3 ), [18] [{(m-h 5 -C 5 H 4 PPh 2 )PtPh} 2 ], [{(m-h 5 -C 5 H 4 PPh 2 )PdMe} 2 ], [19] and [{(m-h 5 -C 5 H 4 PPh 2 )AgA C H T U N G T R E N N U N G (PR 3 )} 2 ] (R = Ph, Et). [20] Phosphane coordination leads to a marked deviation from the coplanar orientation of the Cp and Cht rings that is observed for 2 and 3; [5] the angles subtended at the metal center by the ring centroids are 145.2/145.98 (10 a) and 145.98 (11 a).…”

Section: Resultsmentioning

confidence: 99%

“…CCDC-706212, CCDC-706213, CCDC-706214, CCDC-706215, CCDC-706216, CCDC-706217, CCDC-706218, CCDC-706219, and CCDC-711402 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif (14) 13.4714 (3) 19.3162 (10) 13.5111 (16) 8.1356 (3) 7.7561 (8) 8.0594 (8) 10.9736 (10) b [] 11.6353 (5) 10.1843 (6) 12.3274 (3) 10.2321 (6) 12.4013 (14) 22.9414 (4) 15.5516 (18) 13.8676 (12) 12.2949 (10) c [] 17.0221 (8) 19.1642 (14) 13.5669 (3) 16.2273 (10) 13.5425 (16) 36.6038 (8) 9.8927 (10) 21.887 (2) 13.3191 (12…”

Section: Special Featuresmentioning

confidence: 99%

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Secondary Interactions in Phosphane‐Functionalized Group 4 Cycloheptatrienyl–Cyclopentadienyl Sandwich Complexes

Büschel

Jungton

Bannenberg

et al. 2009

Chemistry A European J

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Twice as reactive: The coordination chemistry of phosphane-functionalized Zr and Hf cycloheptatrienyl-cyclopentadienyl complexes gives rise to unusual secondary interactions associated with the presence of Lewis acidic 16-electron sandwich moieties. These structures can develop weak dative bonds as exemplified by the noncovalent Pd-->Zr interaction in the heterobimetallic {Zr(2)Pd} complex (see picture). Phosphane-functionalized cycloheptatrienyl-cyclopentadienyl Group 4 metal complexes of the type [(eta(7)-C(7)H(7))M(eta(5)-C(5)H(4)PR(2))] (M=Ti (9); M=Zr (10); M=Hf (11); R=Ph (a); R=iPr (b)) have been prepared by the reduction of [(eta(5)-C(5)H(4)PR(2))TiCl(3)] or [(eta(5)-C(5)H(4)PR(2))(2)MCl(2)] (M=Zr, Hf) with magnesium in the presence of cycloheptatriene (C(7)H(8)). In the solid state, the Ti complex 9 a and the complex 11 b are monomeric, whereas 10 a, 10 b, and 11 a form dimers, in which the sandwich units are linked by long Zr-P or Hf-P bonds. Density-functional theory (DFT) calculations indicate that the metal-phosphane interaction is weak, and accordingly, both the Ti complex 9 b and the Zr complex 10 b act as monodentate phosphane ligands upon reaction with [{(cod)RhCl}(2)] (cod=eta(4)-1,5-cyclooctadiene). The X-ray crystal structures of [(cod)Rh(9 b)Cl] (12) and [(cod)Rh(10 b)Cl] (13) reveal that only the latter exhibits a secondary intramolecular Cl-metal interaction. The complex [(10 b)(2)Pd] (14) was obtained by reaction of [(eta(5)-C(5)H(5))Pd(eta(3)-C(3)H(5))] with two equivalents of 10 b. The solid-state structure of 14 reveals a T-shaped Pd(0) center with a long Pd-Zr bond of 2.9709(3) A, which can be interpreted as a weak noncovalent Pd(0)-->Zr(+IV) bond, as indicated by the calculated relaxed force constant of 5.68 N m(-1).

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Section: Resultssupporting

confidence: 71%

Section: Resultsmentioning

confidence: 99%

Section: Special Featuresmentioning

confidence: 99%

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Secondary Interactions in Phosphane‐Functionalized Group 4 Cycloheptatrienyl–Cyclopentadienyl Sandwich Complexes

Büschel

Jungton

Bannenberg

et al. 2009

Chemistry A European J

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“…Solution photochemistry at room temperature formed the dimer [Cp 2 Cr(CO) 2 ] 2 along with CO and H 2 production . The irradiation of (η 5 -C 5 H 4 PPh 2 )CrH(CO) 3 with broadband photolysis was employed as a preparative method to obtain the dimer [(μ,η 5 –C 5 H 4 PPh 2 )Cr(CO) 2 ] 2 , but competition between decarbonylation and dehydrogenation afforded a mixture of products …”

Section: Metal Hydride Photochemistry By Transition Metal Groupmentioning

confidence: 99%

“…When D 2 was employed, H/D exchange was observed for the Cp complex through an isotopic shift of the CpMoD(CO) 2 bands . The photochemical synthesis of the Mo dimer [(μ,η 5 -C 5 H 4 PPh 2 )Mo(CO) 2 ] 2 from (η 5 -C 5 H 4 PPh 2 )MoH(CO) 3 proceeded cleanly . The photoreaction of Cp*MoH(η 6 -C 5 Me 4 CH 2 ) is described together with that of Cp* 2 Mo(H) 2 below.…”

Section: Metal Hydride Photochemistry By Transition Metal Groupmentioning

confidence: 99%

Photochemistry of Transition Metal Hydrides

2016

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Photochemical reactivity associated with metal-hydrogen bonds is widespread among metal hydride complexes and has played a critical part in opening up C-H bond activation. It has been exploited to design different types of photocatalytic reactions and to obtain NMR spectra of dilute solutions with a single pulse of an NMR spectrometer. Because photolysis can be performed on fast time scales and at low temperature, metal-hydride photochemistry has enabled determination of the molecular structure and rates of reaction of highly reactive intermediates. We identify five characteristic photoprocesses of metal monohydride complexes associated with the M-H bond, of which the most widespread are M-H homolysis and R-H reductive elimination. For metal dihydride complexes, the dominant photoprocess is reductive elimination of H2. Dihydrogen complexes typically lose H2 photochemically. The majority of photochemical reactions are likely to be dissociative, but hydride complexes may be designed with equilibrated excited states that undergo different photochemical reactions, including proton transfer or hydride transfer. The photochemical mechanisms of a few reactions have been analyzed by computational methods, including quantum dynamics. A section on specialist methods (time-resolved spectroscopy, matrix isolation, NMR, and computational methods) and a survey of transition metal hydride photochemistry organized by transition metal group complete the Review.

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Tungsten Compounds with CO or Isocyanides

Baker¹,

Brown²

2007

Comprehensive Organometallic Chemistry III

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Transition-metal derivatives of the functionalized cyclopentadienyl ligand. XVI. Synthesis of the bridged complexes [(μ-η5-C5H4PPh2)M(CO)2]2 (M=Cr, Mo, W). X-Ray crystal structure of the dihydride derivative [(μ-η5-C5H4PPh2)W(CO)2H]2

Cited by 7 publications

References 38 publications

Secondary Interactions in Phosphane‐Functionalized Group 4 Cycloheptatrienyl–Cyclopentadienyl Sandwich Complexes

Secondary Interactions in Phosphane‐Functionalized Group 4 Cycloheptatrienyl–Cyclopentadienyl Sandwich Complexes

Photochemistry of Transition Metal Hydrides

Tungsten Compounds with CO or Isocyanides

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