Steric and “Indenyl” Effects in the Chemistry of Alkylidyne Complexes of Tungsten and Molybdenum

Stephen Anderson; Anthony F. Hill; Bashir A. Nasir

doi:10.1021/om00006a049

Steric and “Indenyl” Effects in the Chemistry of Alkylidyne Complexes of Tungsten and Molybdenum

Stephen Anderson, Anthony F. Hill^*, Bashir A. Nasir

^*Corresponding author for this work

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

33 Citations (Scopus)

Abstract

Reaction between LiC₅Me₅ or KC₉H₇ and [M(≡C₆H₃Me2-2,6)(CO)₂(NC₅H₄Me-4)₂Br] affords the complexes [M(≡CC₆H₃Me₂-2,6)(CO)₂L] (L = η-C₅Me₅, M = W (1a); Mo (1b); L = η⁵-C₉H₇, M = Mo (1c)). The complexes 1a and 1b react with PMe3 to give η²-ketenyl compounds [M{η²-C(O)CC₆H₃Me2-2,6}(CO)(PMe₃)(η-C₅Me₅)] (M = W (2a), Mo (2b)) while the reaction of 1c with PMe₃ or P(OMe)₃ gives [Mo(≡CC₆H₃Me2-2,6)(CO)L'(η⁵-C₉H₇)] (L' = PMe₃ (3a), P(OMe)₃ (3b)). Thermolysis of 2a provides 1a rather than the anticipated complex [W(≡CC₆H₃Me2-2,6)(CO)(PMe₃)(η-C₅Me₅)]. Compound lb has been employed to prepare the range of heterobimetallic compounds [MoFe(η-CC₆H₃Me2-2,6)(CO)₅(η-C₅Me₅)] (4), [MoFe(μ-CC₆H₃Me2-2,6)(CO)₃(μ-dppm)(η-C₅Me₅)] (5), [MoFe(μ-η²-SeCC₆H₃Me₂-3,6)(CO)₅-(η-C₅Me₅)] (6), and [MoCu(μ-CC₆H₃Me₂-2,6)(CO)(μ-CO)(η-C₅Me₅)₂] (8b), with bonds between molybdenum and iron or copper supported by the xylylmethylidyne unit, to assess the effects of steric encumbrance on bridge-assisted cluster asembly.

Original language	English
Pages (from-to)	2987-2992
Number of pages	6
Journal	Organometallics
Volume	14
Issue number	6
DOIs	https://doi.org/10.1021/om00006a049
Publication status	Published - Jun 1995
Externally published	Yes

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@article{d8489cd2c56c4f3e81e18a42ed9d320c,

title = "Steric and “Indenyl” Effects in the Chemistry of Alkylidyne Complexes of Tungsten and Molybdenum",

abstract = "Reaction between LiC5Me5 or KC9H7 and [M(≡C6H3Me2-2,6)(CO)2(NC5H4Me-4)2Br] affords the complexes [M(≡CC6H3Me2-2,6)(CO)2L] (L = η-C5Me5, M = W (1a); Mo (1b); L = η5-C9H7, M = Mo (1c)). The complexes 1a and 1b react with PMe3 to give η2-ketenyl compounds [M{η2-C(O)CC6H3Me2-2,6}(CO)(PMe3)(η-C5Me5)] (M = W (2a), Mo (2b)) while the reaction of 1c with PMe3 or P(OMe)3 gives [Mo(≡CC6H3Me2-2,6)(CO)L'(η5-C9H7)] (L' = PMe3 (3a), P(OMe)3 (3b)). Thermolysis of 2a provides 1a rather than the anticipated complex [W(≡CC6H3Me2-2,6)(CO)(PMe3)(η-C5Me5)]. Compound lb has been employed to prepare the range of heterobimetallic compounds [MoFe(η-CC6H3Me2-2,6)(CO)5(η-C5Me5)] (4), [MoFe(μ-CC6H3Me2-2,6)(CO)3(μ-dppm)(η-C5Me5)] (5), [MoFe(μ-η2-SeCC6H3Me2-3,6)(CO)5-(η-C5Me5)] (6), and [MoCu(μ-CC6H3Me2-2,6)(CO)(μ-CO)(η-C5Me5)2] (8b), with bonds between molybdenum and iron or copper supported by the xylylmethylidyne unit, to assess the effects of steric encumbrance on bridge-assisted cluster asembly.",

author = "Stephen Anderson and Hill, {Anthony F.} and Nasir, {Bashir A.}",

year = "1995",

month = jun,

doi = "10.1021/om00006a049",

language = "English",

volume = "14",

pages = "2987--2992",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "6",

}

TY - JOUR

T1 - Steric and “Indenyl” Effects in the Chemistry of Alkylidyne Complexes of Tungsten and Molybdenum

AU - Anderson, Stephen

AU - Hill, Anthony F.

AU - Nasir, Bashir A.

PY - 1995/6

Y1 - 1995/6

N2 - Reaction between LiC5Me5 or KC9H7 and [M(≡C6H3Me2-2,6)(CO)2(NC5H4Me-4)2Br] affords the complexes [M(≡CC6H3Me2-2,6)(CO)2L] (L = η-C5Me5, M = W (1a); Mo (1b); L = η5-C9H7, M = Mo (1c)). The complexes 1a and 1b react with PMe3 to give η2-ketenyl compounds [M{η2-C(O)CC6H3Me2-2,6}(CO)(PMe3)(η-C5Me5)] (M = W (2a), Mo (2b)) while the reaction of 1c with PMe3 or P(OMe)3 gives [Mo(≡CC6H3Me2-2,6)(CO)L'(η5-C9H7)] (L' = PMe3 (3a), P(OMe)3 (3b)). Thermolysis of 2a provides 1a rather than the anticipated complex [W(≡CC6H3Me2-2,6)(CO)(PMe3)(η-C5Me5)]. Compound lb has been employed to prepare the range of heterobimetallic compounds [MoFe(η-CC6H3Me2-2,6)(CO)5(η-C5Me5)] (4), [MoFe(μ-CC6H3Me2-2,6)(CO)3(μ-dppm)(η-C5Me5)] (5), [MoFe(μ-η2-SeCC6H3Me2-3,6)(CO)5-(η-C5Me5)] (6), and [MoCu(μ-CC6H3Me2-2,6)(CO)(μ-CO)(η-C5Me5)2] (8b), with bonds between molybdenum and iron or copper supported by the xylylmethylidyne unit, to assess the effects of steric encumbrance on bridge-assisted cluster asembly.

AB - Reaction between LiC5Me5 or KC9H7 and [M(≡C6H3Me2-2,6)(CO)2(NC5H4Me-4)2Br] affords the complexes [M(≡CC6H3Me2-2,6)(CO)2L] (L = η-C5Me5, M = W (1a); Mo (1b); L = η5-C9H7, M = Mo (1c)). The complexes 1a and 1b react with PMe3 to give η2-ketenyl compounds [M{η2-C(O)CC6H3Me2-2,6}(CO)(PMe3)(η-C5Me5)] (M = W (2a), Mo (2b)) while the reaction of 1c with PMe3 or P(OMe)3 gives [Mo(≡CC6H3Me2-2,6)(CO)L'(η5-C9H7)] (L' = PMe3 (3a), P(OMe)3 (3b)). Thermolysis of 2a provides 1a rather than the anticipated complex [W(≡CC6H3Me2-2,6)(CO)(PMe3)(η-C5Me5)]. Compound lb has been employed to prepare the range of heterobimetallic compounds [MoFe(η-CC6H3Me2-2,6)(CO)5(η-C5Me5)] (4), [MoFe(μ-CC6H3Me2-2,6)(CO)3(μ-dppm)(η-C5Me5)] (5), [MoFe(μ-η2-SeCC6H3Me2-3,6)(CO)5-(η-C5Me5)] (6), and [MoCu(μ-CC6H3Me2-2,6)(CO)(μ-CO)(η-C5Me5)2] (8b), with bonds between molybdenum and iron or copper supported by the xylylmethylidyne unit, to assess the effects of steric encumbrance on bridge-assisted cluster asembly.

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U2 - 10.1021/om00006a049

DO - 10.1021/om00006a049

M3 - Article

AN - SCOPUS:0000613623

SN - 0276-7333

VL - 14

SP - 2987

EP - 2992

JO - Organometallics

JF - Organometallics

IS - 6

ER -

Steric and “Indenyl” Effects in the Chemistry of Alkylidyne Complexes of Tungsten and Molybdenum

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