Mixed-metal cluster chemistry. 29. Core expansion and ligand-driven metal exchange at group 6-iridium clusters

Alistair J. Usher; Nigel T. Lucas; Gulliver T. Dalton; Michael D. Randles; Lydie Viau; Mark G. Humphrey; Simon Petrie; Robert Stranger; Anthony C. Willis; A. David Rae

doi:10.1021/ic061736l

Mixed-metal cluster chemistry. 29. Core expansion and ligand-driven metal exchange at group 6-iridium clusters

Alistair J. Usher
, Nigel T. Lucas
, Gulliver T. Dalton
, Michael D. Randles
, Lydie Viau
, Mark G. Humphrey^*
, Simon Petrie
, Robert Stranger
, Anthony C. Willis
, A. David Rae

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

9 Citations (Scopus)

Abstract

Reactions of the tetrahedral clusters Molr₃(μ-CO) ₃(CO)₈(η-L) (L = C₅HMe₄, C ₅Me₅) with the carbonylmetalate anions [Mo(CO) ₃(η-L)]^- afford the trigonal bipyramidal clusters Mo₂lr₃(μ₃-H)(μ-CO)₂(CO) ₉(η-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 Mlr₃(μ-CO) ₃(CO)₈(η-C₅H₅) (M = Mo, W) with [M(CO)₃(η-L)]^- (L = C₅HMe₄, C₅Me₅) afford the core-expanded heteroapex clusters M ₂lr₃(μ₃-H)(μ-CO)₂(CO) ₉(η-C₅H₅)(η-L) (M = Mo, L = C ₅HMe₄ (5c), 9%, L = C₅Me₅ (5d), 4%; M = W, L = C₅Me₅ (6d), 5%) in low yield, together with the homoapex clusters M₂lr₃(μ₃-H)(μ-CO) ₂(CO)₉(η-L)₂ (M = Mo, L = C ₅HMe₄ (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 Molr₃(μ-CO) ₃(CO)₈(η-C₅Me₅) and [M(CO) ₃(η-C₅H₅)]^-. Treating Molr ₃(μ-CO)₃(CO)₈(η-C₅H ₅) with 1 equiv of [M(CO)₃(η-C₅Me ₅)]^- affords 5d as the major product, a further 1 equiv affording some Molr₃(μ-CO)₃(CO)₈(η- C₅-Me₅) 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.

Original language	English
Pages (from-to)	10859-10872
Number of pages	14
Journal	Inorganic Chemistry
Volume	45
Issue number	26
DOIs	https://doi.org/10.1021/ic061736l
Publication status	Published - 25 Dec 2006

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@article{f85374407ea5461f898cdfb2cd2cffae,

title = "Mixed-metal cluster chemistry. 29. Core expansion and ligand-driven metal exchange at group 6-iridium clusters",

abstract = "Reactions of the tetrahedral clusters Molr3(μ-CO) 3(CO)8(η-L) (L = C5HMe4, C 5Me5) with the carbonylmetalate anions [Mo(CO) 3(η-L)]- afford the trigonal bipyramidal clusters Mo2lr3(μ3-H)(μ-CO)2(CO) 9(η-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 Mlr3(μ-CO) 3(CO)8(η-C5H5) (M = Mo, W) with [M(CO)3(η-L)]- (L = C5HMe4, C5Me5) afford the core-expanded heteroapex clusters M 2lr3(μ3-H)(μ-CO)2(CO) 9(η-C5H5)(η-L) (M = Mo, L = C 5HMe4 (5c), 9\%, L = C5Me5 (5d), 4\%; M = W, L = C5Me5 (6d), 5\%) in low yield, together with the homoapex clusters M2lr3(μ3-H)(μ-CO) 2(CO)9(η-L)2 (M = Mo, L = C 5HMe4 (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 Molr3(μ-CO) 3(CO)8(η-C5Me5) and [M(CO) 3(η-C5H5)]-. Treating Molr 3(μ-CO)3(CO)8(η-C5H 5) with 1 equiv of [M(CO)3(η-C5Me 5)]- affords 5d as the major product, a further 1 equiv affording some Molr3(μ-CO)3(CO)8(η- C5-Me5) 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.",

author = "Usher, \{Alistair J.\} and Lucas, \{Nigel T.\} and Dalton, \{Gulliver T.\} and Randles, \{Michael D.\} and Lydie Viau and Humphrey, \{Mark G.\} and Simon Petrie and Robert Stranger and Willis, \{Anthony C.\} and Rae, \{A. David\}",

year = "2006",

month = dec,

day = "25",

doi = "10.1021/ic061736l",

language = "English",

volume = "45",

pages = "10859--10872",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "26",

}

TY - JOUR

T1 - Mixed-metal cluster chemistry. 29. Core expansion and ligand-driven metal exchange at group 6-iridium clusters

AU - Usher, Alistair J.

AU - Lucas, Nigel T.

AU - Dalton, Gulliver T.

AU - Randles, Michael D.

AU - Viau, Lydie

AU - Humphrey, Mark G.

AU - Petrie, Simon

AU - Stranger, Robert

AU - Willis, Anthony C.

AU - Rae, A. David

PY - 2006/12/25

Y1 - 2006/12/25

N2 - Reactions of the tetrahedral clusters Molr3(μ-CO) 3(CO)8(η-L) (L = C5HMe4, C 5Me5) with the carbonylmetalate anions [Mo(CO) 3(η-L)]- afford the trigonal bipyramidal clusters Mo2lr3(μ3-H)(μ-CO)2(CO) 9(η-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 Mlr3(μ-CO) 3(CO)8(η-C5H5) (M = Mo, W) with [M(CO)3(η-L)]- (L = C5HMe4, C5Me5) afford the core-expanded heteroapex clusters M 2lr3(μ3-H)(μ-CO)2(CO) 9(η-C5H5)(η-L) (M = Mo, L = C 5HMe4 (5c), 9%, L = C5Me5 (5d), 4%; M = W, L = C5Me5 (6d), 5%) in low yield, together with the homoapex clusters M2lr3(μ3-H)(μ-CO) 2(CO)9(η-L)2 (M = Mo, L = C 5HMe4 (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 Molr3(μ-CO) 3(CO)8(η-C5Me5) and [M(CO) 3(η-C5H5)]-. Treating Molr 3(μ-CO)3(CO)8(η-C5H 5) with 1 equiv of [M(CO)3(η-C5Me 5)]- affords 5d as the major product, a further 1 equiv affording some Molr3(μ-CO)3(CO)8(η- C5-Me5) 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.

AB - Reactions of the tetrahedral clusters Molr3(μ-CO) 3(CO)8(η-L) (L = C5HMe4, C 5Me5) with the carbonylmetalate anions [Mo(CO) 3(η-L)]- afford the trigonal bipyramidal clusters Mo2lr3(μ3-H)(μ-CO)2(CO) 9(η-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 Mlr3(μ-CO) 3(CO)8(η-C5H5) (M = Mo, W) with [M(CO)3(η-L)]- (L = C5HMe4, C5Me5) afford the core-expanded heteroapex clusters M 2lr3(μ3-H)(μ-CO)2(CO) 9(η-C5H5)(η-L) (M = Mo, L = C 5HMe4 (5c), 9%, L = C5Me5 (5d), 4%; M = W, L = C5Me5 (6d), 5%) in low yield, together with the homoapex clusters M2lr3(μ3-H)(μ-CO) 2(CO)9(η-L)2 (M = Mo, L = C 5HMe4 (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 Molr3(μ-CO) 3(CO)8(η-C5Me5) and [M(CO) 3(η-C5H5)]-. Treating Molr 3(μ-CO)3(CO)8(η-C5H 5) with 1 equiv of [M(CO)3(η-C5Me 5)]- affords 5d as the major product, a further 1 equiv affording some Molr3(μ-CO)3(CO)8(η- C5-Me5) 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.

UR - https://www.scopus.com/pages/publications/33846518301

U2 - 10.1021/ic061736l

DO - 10.1021/ic061736l

M3 - Article

SN - 0020-1669

VL - 45

SP - 10859

EP - 10872

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 26

ER -

Mixed-metal cluster chemistry. 29. Core expansion and ligand-driven metal exchange at group 6-iridium clusters

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