Studies of metal exchange reactions: the synthesis and structures of heteronuclear metal clusters containing the indenyl ligand (μ3-CR)Co2M(CO)8(η5- Ind)(R=H,CH3,C6H5,COOC2H5; M=Mo,W)

Zhang, Weiqiang; Zhu, Bilan; Hu, Bin; Zhang, Yuhua; Zhao, Quanyi; Yin, Yuan‐Qi

doi:10.1016/j.jorganchem.2003.11.028

Cited by 6 publications

(1 citation statement)

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“…Almost all examples of metal exchange thus far have involved replacement of one ligated metal fragment with another containing a different metal atom, but low-yielding exceptions (i.e., corresponding to a formal ligand exchange only) have been noted: MoCo 2 (μ 3 -CR)(CO) 8 {η-C 5 H 4 C(O)Me} (R = Ph, CO 2 Et) reacts with [Mo(CO) 3 (η 5 -L)] - (L = C 9 H 7 , C 5 H 5 ) to afford MoCo 2 (μ 3 -CR)(CO) 8 (η 5 -L) (7−47%), , the linked diclusters {MoCo 2 (μ 3 -CR)(CO) 8 } 2 (μ-C 5 H 4 C(O)C 6 H 4 -4-C(O)C 5 H 4 ) (R = CO 2 Et, Ph) react with [Mo(CO) 3 (η-C 5 H 4 R‘)] - (R‘ = H, C(O)Me, CO 2 Et) to give vertex-exchanged monoclusters (30−39%), and linked diclusters react with linked dicluster dianions to give mixtures of linked mono-, di-, and tricluster species …”

Section: Introductionmentioning

confidence: 99%

Mixed-Metal Cluster Chemistry. 29. Core Expansion and Ligand-Driven Metal Exchange at Group 6−Iridium Clusters¹

et al. 2006

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Reactions of the tetrahedral clusters MoIr3(mu-CO)3(CO)8(eta-L) (L = C5HMe4, C5Me5) with the carbonylmetalate anions [Mo(CO)3(eta-L)]- afford the trigonal bipyramidal clusters Mo2Ir3(mu3-H)(mu-CO)2(CO)9(eta-L)2 (L = C5HMe4 (3c), 74%; L = C5Me5 (3d), 55%) in which the group 6 metal atoms occupy the apexes; reaction of the cyclopentadienylmolybdenum-containing analogues or their cyclopentadienyltungsten-containing homologues failed to afford analogous products. Reactions of MIr3(mu-CO)3(CO)8(eta-C5H5) (M = Mo, W) with [M(CO)3(eta-L)]- (L = C5HMe4, C5Me5) afford the core-expanded heteroapex clusters M2Ir3(mu3-H)(mu-CO)2(CO)9(eta-C5H5)(eta-L) (M = Mo, L = C5HMe4 (5c), 9%, L = C5Me5 (5d), 4%; M = W, L = C5Me5 (6d), 5%) in low yield, together with the homoapex clusters M2Ir3(mu3-H)(mu-CO)2(CO)9(eta-L)2 (M = Mo, L = C5HMe4 (3c), 81%, L = C5Me5 (3d), 60%; M = W, L = C5Me5 (4d), 5%) in much higher yield for the Mo-containing examples. The identities of clusters 3c,d, 4d, and 5c,d have been confirmed by single-crystal X-ray diffraction studies, with the same disposition of ligands about the trigonal bipyramidal cluster cores being observed in each case, a ligand arrangement that has been examined by complementary density functional theory studies. While cluster 5d is accessible as above, no reaction is observed from MoIr3(mu-CO)3(CO)8(eta-C5Me5) and [M(CO)3(eta-C5H5)]-. Treating MoIr3(mu-CO)3(CO)8(eta-C5H5) with 1 equiv of [M(CO)3(eta-C5Me5)]- affords 5d as the major product, a further 1 equiv affording some MoIr3(mu-CO)3(CO)8(eta-C5Me5) and a third 1 equiv giving a good yield of 3d. This is consistent with reaction proceeding by apex fragment addition, followed by apex fragment elimination, and finally a further apex fragment addition, the homometallic incoming apexes being distinguished from the departing vertices by their highly methylated cyclopentadienyl ligands. Spectroscopic data suggest that the electron density at these disparate-metal-containing cluster cores is tunable by progressive (conceptual) cyclopentadienyl alkylation.

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Section: Introductionmentioning

confidence: 99%

Mixed-Metal Cluster Chemistry. 29. Core Expansion and Ligand-Driven Metal Exchange at Group 6−Iridium Clusters¹

et al. 2006

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Diphosphine Substitution and Carbyne Ligand Transfer in the Reaction of 2,3-Bis(diphenylphosphino)maleic Anhydride (bma) with the Methylidyne-capped Clusters HCCo2MCp(CO)8 (where M=Mo, W): Synthesis and X-ray Diffraction Structures of the Vinylidene-bridged Clusters Co2MCp(CO)6[μ–C=C(H)CH2C(PPh2)C(PPh2)C(O)OC(O)]

Zhang¹,

Watson²,

Richmond³

2008

J Chem Crystallogr

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Molybdenum Compounds with CO or Isocyanides

Tamm

Baker

2007

Comprehensive Organometallic Chemistry III

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Studies of metal exchange reactions: the synthesis and structures of heteronuclear metal clusters containing the indenyl ligand (μ3-CR)Co2M(CO)8(η5- Ind)(R=H,CH3,C6H5,COOC2H5; M=Mo,W)

Cited by 6 publications

References 41 publications

Mixed-Metal Cluster Chemistry. 29. Core Expansion and Ligand-Driven Metal Exchange at Group 6−Iridium Clusters¹

Mixed-Metal Cluster Chemistry. 29. Core Expansion and Ligand-Driven Metal Exchange at Group 6−Iridium Clusters¹

Molybdenum Compounds with CO or Isocyanides

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Studies of metal exchange reactions: the synthesis and structures of heteronuclear metal clusters containing the indenyl ligand (μ3-CR)Co2M(CO)8(η5- Ind)(R=H,CH3,C6H5,COOC2H5; M=Mo,W)

Cited by 6 publications

References 41 publications

Mixed-Metal Cluster Chemistry. 29. Core Expansion and Ligand-Driven Metal Exchange at Group 6−Iridium Clusters1

Mixed-Metal Cluster Chemistry. 29. Core Expansion and Ligand-Driven Metal Exchange at Group 6−Iridium Clusters1

Molybdenum Compounds with CO or Isocyanides

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Mixed-Metal Cluster Chemistry. 29. Core Expansion and Ligand-Driven Metal Exchange at Group 6−Iridium Clusters¹

Mixed-Metal Cluster Chemistry. 29. Core Expansion and Ligand-Driven Metal Exchange at Group 6−Iridium Clusters¹