μ2 Bridging carbonyl systems in transition metal complexes

Colton, R.; McCormick, Malcolm J.

doi:10.1016/s0010-8545(00)80365-3

Cited by 103 publications

(35 citation statements)

References 148 publications

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“…In all cases crystalline products were obtained and representative examples of these have been characterized structurally by X-ray analysis. These analyses confirm the presence of direct Mo-Rh and Mo-Cu bonds in these compounds in addition to carbonyl groups in a number of different bonding environments (23)(24)(25)(26).…”

Section: Resultssupporting

confidence: 63%

“…Obviously the interaction is of a semi-bridging type since the Mo-C-0 angles are not far removed from linear. Numerous recent publications have documented and discussed different types of bridging CO interactions in heterobimetallic transition metal complexes (23)(24)(25)(26)(27)(28)(29)(30)(31)34,36). The present Cu compound does not appear to fit into the category of a distal electron-rich metal centre (the Cu centre has a 14-electron count) donating excessive charge into the CO IT* orbitals (25), although, if IT-IT bonding occurs between the Cu and the Mo centres, then an interaction with the CO groups similar to that postulated for the complex ( T ( -C~H~)~M O~( C O )~ (26,39) may be possible.…”

Section: Resultsmentioning

confidence: 99%

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Synthesis and characterization of LMo(CO)₃M(PPh₃)_x (where L = tridentate pyrazolyl-gallate or -borate ligand; M = Rh, x = 2; M = Cu, x = 1). X-ray crystal structures of [MeGapz₃]Mo(CO)₃Rh(PPh₃)₂ and [MeGapz₃]Mo(CO)₃Cu(PPh₃) (where pz = pyrazolyl, N₂C₃H₃)

Banta¹,

Louie²,

Onyiriuka³

et al. 1986

Can. J. Chem.

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. Can. J. Chem. 64, 373 (1986).The reactions of the LMo(CO),-ions (L = MeGapz,, HBpz3, Me2Gapz(OCH2CH2NMe2)) with [Cu(PPh3)C1I4 and Rh(PPh3),C1 have yielded complexes with Mo-Cu and Mo-Rh bonds. The X-ray crystal structures of two such complexes have been determined. Crystals of [MeGap~~lMo(C0)~Cu(PPh~) are monoclinic, a = 17.071(2), b = 16.738(1), c = 23.641 (3) A, P = 104.899(6)", Z = 8, space group P2,/n, and those of [MeGap~~lMo(C0)~Rh(PPh~)~, aretriclinic, a = 12.519(3), b = 17.182(4),c = 12.071(2)A, a = 105.02(1), P = 109.87(1), y = 97.10(2)O,Z = 2,spacegroupPl. Bothstructuresweresolved by conventional heavy atom methods and were refined by full-matrix least-squares procedures to R = 0.040 and R,, = 0.035 for 6296 reflections with I 2 2o(4 and R = 0.036 and R, = 0.037 for 5642 reflections with I 2 3o(4, respectively. The former complex provides a rare example of a 3:3: 1, or capped octahedral structure, with a short (mean) Mo-Cu distance of 2.5 13(9) A.The latter compound displays one terminal and two bridging CO ligands and a Mo-Rh distance of 2.6066(5) A. IntroductionTetrahydrofuran(THF), benzene, CH2C12, and hexane were dried byThe anionic, symmetrical, tridentate &elating rnethy1tris(lrefluxing over Na/benzophenone, potassium, CaH2 and CaS04, respectively, followed by distillation. Rh (PPh3) tered. Evaporation of the solvent from the filtrate gave an oily red-black material which was recrystalllzed from CH2C12/hexane to give air- Experimental stable dark-red crystals of the desired products in approximately 60% Starting mater~alsyield. Analytical, ir, nmr, and other data for the three complexes are Air-sensitive materials were handled in a nitrogen atmosphere. collected in Table 1 and the 'H nmr spectrum for the [MeGapz,]Mo-(C0)3Rh(PPh3)2 complex is shown in Fig. 1. The mass spectrum of this 'Author to whom correspondence may be addressed.latter complex displayed signals due to the P-PP~,+ ion at -890. In the preparationof [HBp~,jMo(co)~Rh(PPh~)~ a yellow crystalline sample of the complex (Ph3P)2Rh(CO)Cl Anal. calcd.: C 64.31, H 4.34; found: C 63.73, H 4.27; vco 1980 cm-' (CH2C12)) was also isolated in low yield. Synthesis of [ M~G U~Z~] M O ( C O )~C U P P~~A solution of the ~a ' [~e~a~z~] M o ( C 0 )~-salt in THF was prepared as described above. A one-quarter molar amount of [Cu(PPh3)C1I4 was added to the reaction mixture and produced an immediate rusty-orange colour. This reaction mixture was stirred for approximately 1 day before the removal of solvent in vacuo. The resulting orange residue was extracted with CH,C12 and the mixture filtered. Hexane was added to the filtrate and the mixed solvents allowed to evaporate slowly. Goldenyellow air-stable crystals of the product, [MeGap~,jMo(C0)~CuPPh~ were produced from the concentrated solutions in approximately 60% yield. Pertinent physical data are included in Table 1 for the complex.X-ray crystallographic analyses [Methyltris(l -pyrazolyl) )' with S = r a n count

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Section: Resultssupporting

confidence: 63%

Section: Resultsmentioning

confidence: 99%

Synthesis and characterization of LMo(CO)₃M(PPh₃)_x (where L = tridentate pyrazolyl-gallate or -borate ligand; M = Rh, x = 2; M = Cu, x = 1). X-ray crystal structures of [MeGapz₃]Mo(CO)₃Rh(PPh₃)₂ and [MeGapz₃]Mo(CO)₃Cu(PPh₃) (where pz = pyrazolyl, N₂C₃H₃)

Banta¹,

Louie²,

Onyiriuka³

et al. 1986

Can. J. Chem.

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“…The nonbridged distances of 2.721 (2), 2.729 (2) and 2.720 (2) A are shorter than the bridged distances of 2.772(2), 2.775 (2) and 2.745 (2)/~. This is remarkable, since, within a particular compound, carbonyl-bridged metal-metal distances have always been found to be shorter than noncarbonyl-bridged metal-metal distances (Colton & McCormick, 1980). Evidently, diop, which cobridges two Ir atoms with a carbonyl, imposes geometric constraints on the Ir atoms in the basal plane.…”

Section: Resultsmentioning

confidence: 86%

Structure of a tetrairidium cluster with a bridging diop ligand: 2,3-μ-[(+)-4,5-bis(diphenylphosphinomethyl)-2,2-dimethyl-1,3-dioxolane]-(P,P')-2,3;3,4;4,2-tri-μ-carbonyl-1,1,1,2,3,4,4-heptacarbonyl-tetrahedro-tetrairidium

Tranqui¹,

Durif²,

Eddine³

et al. 1982

Acta Crystallogr Sect B

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The crystal structure of Ir4(CO)10 { (+)-diop }, C4~H32Ir4O12P 2, has been determined. The cluster crystallizes in the space group P212~21, with a = 12.009 (3), b = 16.943 (6) and c = 20.823 (8)A. The structure was refined to R l = 0.045 and R 2 = 0.052 for 1875 reflections. The diop ligand adopts an unusual configuration and bridges two Ir atoms, forming an eight-membered ring r--Ir-Ir-P-C4-P-q. Ir atoms edge-bridged by carbonyl ligands have a mean Ir-Ir distance of 2.764 (2)A, which is significantly longer than the mean Ir-Ir distance of 2.723 (2)A for non-carbonyl-bridged atoms.

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“…2.999(2) A), which indicate a compression along the Ir-Ir axis due to mutual attraction of the metals. The geometry of the bridging carbonyl ligand is typical for such a group accompanied by a metal-metal bond (14), therefore the Ir(1)-C(3)-Ir (2) angle, of 81.9(3)" is acute. Both terminal carbonyl groups are normal, with Ir-C distances much shorter than those on the bridging group.…”

Section: Description Of Structure and Discussionmentioning

confidence: 99%

The structure of [Ir₂(CO)₂(μ-H)(μ-CO)(Ph₂PCH₂PPh₂)₂][BF₄] and comparisons with its rhodium analogue and other related doubly bridged A-frames

Sutherland¹,

Cowie²

1986

Can. J. Chem.

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. 64, 464 (1986).The structure of [Ir2(CO)2(p-H)(p-CO)(DPM)2][BF4] (DPM=Ph2PCH2PPh2) has been determined~crystallographically. It crystallizes in the monoclinic space group P2' /n (a = 13.7740(6) A, b = 15.277(2) A, c = 23.581 (2) A, P = 97.015(5)", V = 4924.9 A3, Z =4) and on the basis of 6628 unique observations and variation of 272 parameters, the structure converged to R = 0.031 and R,, = 0.043. This metal-metal bonded complex is similar to its rhodium analogue, having the two essentially identical Ir centres bridged by the carbonyl, hydride, and two diphosphine ligands. The major difference between this compound and the rhodium species (in the solid state) relates to the orientation of the phenyl groups of the diphosphine ligands; in the iridium complex four of these groups block the sites adjacent to the bridging hydride ligand, whereas these sites are relatively unobstructed in the rhodium analogue. This difference may result in different coordination sites for substrate molecules and therefore in different chemistry. IntroductionWe have recently shown (1) that catalysis of the water-gas shift (WGS) reaction, by complexes containing two metal centres, can be effectively modelled by using DPM-bridged (DPM = Ph2PCH2PPh2), hydrido, and hydroxy complexes of iridium. In particular, the observation of [Ir2(C0)2(pH)(k-CO)(DPMh]+ in our WGS cycle prompted us to suggest that this cycle could serve as a model for the one in which the rhodium analogue, [Rh2(C0)2(pH)(pCO)(DPM)2]

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μ2 Bridging carbonyl systems in transition metal complexes

Cited by 103 publications

References 148 publications

Synthesis and characterization of LMo(CO)₃M(PPh₃)_x (where L = tridentate pyrazolyl-gallate or -borate ligand; M = Rh, x = 2; M = Cu, x = 1). X-ray crystal structures of [MeGapz₃]Mo(CO)₃Rh(PPh₃)₂ and [MeGapz₃]Mo(CO)₃Cu(PPh₃) (where pz = pyrazolyl, N₂C₃H₃)

Synthesis and characterization of LMo(CO)₃M(PPh₃)_x (where L = tridentate pyrazolyl-gallate or -borate ligand; M = Rh, x = 2; M = Cu, x = 1). X-ray crystal structures of [MeGapz₃]Mo(CO)₃Rh(PPh₃)₂ and [MeGapz₃]Mo(CO)₃Cu(PPh₃) (where pz = pyrazolyl, N₂C₃H₃)

Structure of a tetrairidium cluster with a bridging diop ligand: 2,3-μ-[(+)-4,5-bis(diphenylphosphinomethyl)-2,2-dimethyl-1,3-dioxolane]-(P,P')-2,3;3,4;4,2-tri-μ-carbonyl-1,1,1,2,3,4,4-heptacarbonyl-tetrahedro-tetrairidium

The structure of [Ir₂(CO)₂(μ-H)(μ-CO)(Ph₂PCH₂PPh₂)₂][BF₄] and comparisons with its rhodium analogue and other related doubly bridged A-frames

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μ2 Bridging carbonyl systems in transition metal complexes

Cited by 103 publications

References 148 publications

Synthesis and characterization of LMo(CO)3M(PPh3)x (where L = tridentate pyrazolyl-gallate or -borate ligand; M = Rh, x = 2; M = Cu, x = 1). X-ray crystal structures of [MeGapz3]Mo(CO)3Rh(PPh3)2 and [MeGapz3]Mo(CO)3Cu(PPh3) (where pz = pyrazolyl, N2C3H3)

Synthesis and characterization of LMo(CO)3M(PPh3)x (where L = tridentate pyrazolyl-gallate or -borate ligand; M = Rh, x = 2; M = Cu, x = 1). X-ray crystal structures of [MeGapz3]Mo(CO)3Rh(PPh3)2 and [MeGapz3]Mo(CO)3Cu(PPh3) (where pz = pyrazolyl, N2C3H3)

Structure of a tetrairidium cluster with a bridging diop ligand: 2,3-μ-[(+)-4,5-bis(diphenylphosphinomethyl)-2,2-dimethyl-1,3-dioxolane]-(P,P')-2,3;3,4;4,2-tri-μ-carbonyl-1,1,1,2,3,4,4-heptacarbonyl-tetrahedro-tetrairidium

The structure of [Ir2(CO)2(μ-H)(μ-CO)(Ph2PCH2PPh2)2][BF4] and comparisons with its rhodium analogue and other related doubly bridged A-frames

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Synthesis and characterization of LMo(CO)₃M(PPh₃)_x (where L = tridentate pyrazolyl-gallate or -borate ligand; M = Rh, x = 2; M = Cu, x = 1). X-ray crystal structures of [MeGapz₃]Mo(CO)₃Rh(PPh₃)₂ and [MeGapz₃]Mo(CO)₃Cu(PPh₃) (where pz = pyrazolyl, N₂C₃H₃)

Synthesis and characterization of LMo(CO)₃M(PPh₃)_x (where L = tridentate pyrazolyl-gallate or -borate ligand; M = Rh, x = 2; M = Cu, x = 1). X-ray crystal structures of [MeGapz₃]Mo(CO)₃Rh(PPh₃)₂ and [MeGapz₃]Mo(CO)₃Cu(PPh₃) (where pz = pyrazolyl, N₂C₃H₃)

The structure of [Ir₂(CO)₂(μ-H)(μ-CO)(Ph₂PCH₂PPh₂)₂][BF₄] and comparisons with its rhodium analogue and other related doubly bridged A-frames