Molecular oxygen as a bridging ligand in a transition metal complex

Bennett, M. J.; Donaldson, Peter B.

doi:10.1021/ja00742a048

Cited by 57 publications

(15 citation statements)

References 2 publications

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“…The P(1)−N(1) distance of 1.61(1) Å in the complex is within the range found for a coordinated iminophosphoranyl group . The directly bound Rh−P III distance of 2.206(4) Å also lies within the range found in many Rh(I) phosphine complexes of the type P 2 Rh(CO)Cl. − The molecule has C 2 symmetry with the two fluorine atoms and the carbons to which they are attached being located on a crystallographic 2-fold axis. These two F atoms, the two CN groups, and two imine N atoms are coplanar with the fluoroaromatic ring.…”

Section: Resultssupporting

confidence: 61%

New Heteromultifunctional Fluoroaromatic Bis(phosphinimine) Ligands and Their Complexes. Synthesis and Characterization of New Ligands (Including X-ray Structures of 4,6-(CN)₂C₆F₂-1-(NP(Ph)₂CH₂PPh₂)-3-(NPPh₃) and 4,6-(CN)₂C₆F₂-1,3-bis(NP(Ph)₂CH₂PPh₂)) and Their Rhodium(I) Complexes, Including the Structure of the Novel Dimetallic Complex 4,6-(CN)₂C_6<

McDonald

Cavell

1996

Organometallics

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Reaction of 1,3-dicyanotetrafluorobenzene with trimethylsilyl phosphinimines proceeds through stepwise substitution on the fluoroaromatic to yield mono-and ultimately disubstituted derivatives of the form 4,6-(CN) 2 C 6 F 2 -1-A-3-B. Two molar equivalents of a bifunctional phosphinophosphoranimines, Me 3 SiNP(Ph) 2 CH 2 PPh 2 , result in a dual substitution giving 1 (A ) B ) (NdP(Ph) 2 CH 2 PPh 2 )), whereas 1 equiv of the trimethylsilyl phosphinimine gives the monosubstituted derivative. Treatment of the monosubstituted derivative with a second 1 equiv of the same or a different phosphinimine gives doubly substituted derivatives which can have the same or different phosphorus substituents, e.g. and 2, 4,6-), have been structurally characterized. In 1, the P(1)dN(1) bond length is 1.581(3) Å, the P(3)dN(2) bond length is 1.569(4) Å, the P(1)-N(1)-C(6) angle is 132.1(3)°, and the P(3)-N(2)-C(2) angle is 133.2(3)°. For 2, the P(2)dN(1) bond length (in the Ph 3 PdN unit) is 1.578(4) Å, the P(3)dN(2) bond length in the Ph 2 PCH 2 Ph 2 PdN unit) is 1.585(4) Å, the P(2)-N(1)-C(2) angle is 134.7(4)°, and the P(3)-N(2)-C(6) angle is 129.9-(4)°. 2 reacted readily with [Rh(CO) 2 Cl] 2 to form the mono metallic chelated Rh complex 4, 4,6-(CN) 2 C 6 F 2 -3-(NdPPh 3 )-1-(NdP(Ph) 2 CH 2 P(Ph) 2 Rh(CO)Cl). 1 reacts with both 1 equiv and 0.5 equiv of [Rh(CO) 2 Cl] 2 to form respectively 4,6-(CN) 2 C 6 F 2 -1,3-bis(NdP(Ph) 2 CH 2 P(Ph) 2 Rh-(CO)Cl), 5, and 4,6-(CN) 2 C 6 F 2 -1,3-bis(NdP(Ph) 2 CH 2 P(Ph) 2 )Rh(CO)Cl, 6. The half-metalated complex 6 can be converted to 5 with a second aliquot of the Rh precursor, and the dimetalated complex 5 can be converted to the half-metalated complex 6 by reaction of 5 with more ligand. The bis(phosphine) chelate structure of 6, the dimetalated complex, was deduced from the complex second-order 31 P NMR spectrum solved by simulation. The two P III are trans coordinated to the Rh center, and the two N are not coordinated. There is no P III -P III or P V -P V coupling, but each P III is coupled to two magnetically inequivalent P V . Structural characterization of the dimetalated complex 5 shows a symmetrically substituted complex containing two Rh centers with a square planar geometry around each Rh(I) with the CO cis to the phosphine. Bond angles and lengths are typical for the Rh(I) square planar chelate complex structures. The P(1)-N(1) distance of 1.61(1) Å in the complex is normal for a coordinated iminophosphoranyl group. The directly bound Rh-P III distance of 2.206-(4) Å also lies within the range found in many Rh(I) phosphine complexes of this type.

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Section: Resultssupporting

confidence: 61%

New Heteromultifunctional Fluoroaromatic Bis(phosphinimine) Ligands and Their Complexes. Synthesis and Characterization of New Ligands (Including X-ray Structures of 4,6-(CN)₂C₆F₂-1-(NP(Ph)₂CH₂PPh₂)-3-(NPPh₃) and 4,6-(CN)₂C₆F₂-1,3-bis(NP(Ph)₂CH₂PPh₂)) and Their Rhodium(I) Complexes, Including the Structure of the Novel Dimetallic Complex 4,6-(CN)₂C_6<

McDonald

Cavell

1996

Organometallics

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“…between the rhodium-chlorine bond lengths observed in the " P' represents triphenylphosphine. 6 Related by symmetry to the value above. c L = (C6H5)2P(C3H6)2P(C6HS).…”

Section: Discussionmentioning

confidence: 99%

Crystal and molecular structure of the orange and red allotropes of chlorotris(triphenylphosphine)rhodium(I)

Bennett¹,

Donaldson²

1977

Inorg. Chem.

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“…(r:-CsHs)-(r/3-C4F6)2WC1, 2.417 (3)A, (Davidson, Green, Stone & Welch, 1976) and (r/5-CsHs)(NO)2WC1, 2.386 A, (Greenhough, Kolthammer, Legzdins & Trotter, 1980)]. The W-P distance, 2.516 (3) A, is substantially smaller than the value predicted by the sum of covalent radii, 2.69A, (Pauling, 1960;Bennett & Simpson, 1971), and may suggest significant zr character in the W-P bond from dzr-drc back donation. The P and CI ligands are almost coplanar with the W atom displaced only 1.15 (1)A out of the plane towards the arene group in contrast to Mo(CH3)2(r/6-C6H6)[PC6H 5-(CH3)2] 2 and Mo(CHa)2(r]6-C6HsCH3)[PC6Hs(CH3)2]2 where phosphine ligands are bent much further from the arene plane than the methyls [C(1)-Mo-C(2) 140.7 (3) and 142.4 (1) ° and P(1)-Mo-P(2) 100.6 (1) and 100.2 (1) ° (Atwood et al, 1979)] providing indirect evidence for the location of the hydrido ligand in (IV).…”

Section: Introductionmentioning

confidence: 96%

The structures of mono- and bis-arene tungsten derivatives: (I) bis(η6-toluene)tungsten, (II) hydridobis(η6-toluene)tungsten hexafluorophosphate, (III) hydridobis(η6-monofluorobenzene)tungsten hexafluorophosphate, (IV) dichlorohydrido(η6-toluene)bis(trimethylphosphine)tungsten hexafluorophosphate, (V) bis(acetonitrile)(η3-allyl)(η6-toluene)tungsten hexafluorophosphate

Prout¹,

Gourdon²,

Couldwell³

et al. 1982

Acta Crystallogr Sect B

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Molecular oxygen as a bridging ligand in a transition metal complex

Cited by 57 publications

References 2 publications

Crystal and molecular structure of the orange and red allotropes of chlorotris(triphenylphosphine)rhodium(I)

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