Synthesis and Reactions of Ynol Ester Complexes of Molybdenum and Tungsten: Cleavage of the RCCO-C(O)R′ Bond and of the RCC-OC(O)R′ Bond of Ynol Ester Ligands

Kimberly A. Belsky; Marianna F. Asaro; Sylvia Y. Chen; Andreas Mayr

doi:10.1021/om00041a027

Synthesis and Reactions of Ynol Ester Complexes of Molybdenum and Tungsten: Cleavage of the RCCO-C(O)R′ Bond and of the RCC-OC(O)R′ Bond of Ynol Ester Ligands

Kimberly A. Belsky
, Marianna F. Asaro
, Sylvia Y. Chen
, Andreas Mayr

Chemistry

Stony Brook University

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

11 Scopus citations

Abstract

Reaction of the ketenyl complexes NEt₄[M(η²-RCCO)(S₂CNR″₂)₂(CO)] (3, M = Mo, R = Ph, R″ = Et; 4, M = W, R = Ph, R″ = Et (a), R = C₆H₄CMe₃-4, R″ = Et (b), R = Ph, R″ = Me (c)) and K[W(η²-4-Me₃C-C₆H₄CCO)(N₂C₆H₇)₂(CO)] (5) with acyl halides R′COCl (or R′COBr) affords the (ynol ester)metal complexes [M(S₂CNR″)₂(CO)(η²-RCCOCOR′)] (8: M = Mo, R = Ph, R′ = Ph, R″ = Et) (9: M = W, R = Ph, R′ = Me (a), Ph (b), CHCH₂ (c), trans-CHCHMe (d), trans-CHCHPh (e), R″ = Et; R = C₆H₄CMe₃-4, R′ = Me (f), CH₂Ph (g), CMe₃ (h), R″ = Et; R = Ph, R′ = CMe₃, R″ = Me (i)) and [W(N₂C₆H₇)₂-(CO)(η²-4-Me₃C-C₆H₄CCOCORO] (10: R = C₆H₄CMe₃-4, R′ = CMe₃ (a), CH₂Ph (b), C₆H₄-OMe-4 (c)). Reaction of the ynol ester complexes [W(S₂CNEt₂)₂(CO)(η²-4-Me₃C-C₆H₄CCOCOCH₂R)] (R = H (9f), Ph (9g)) with dimethylamine affords the ketenyl complex [H₂NMe₂] [W(η²-4-Me₃C-C₆H₄CCO) (S₂CNEt₂)₂(CO)]. The ynol ester complexes [W(LL)₂(CO)(η²-4-Me₃C-C₆H₄CCOCOCH₂Ph)] (LL = S₂CNEt₂ (9g), N₂C₆H₇ (10b)) react with NaN(SiMe₃)₂ to give the ketenyl complexes Na[W(η²-4-Me₃C-C₆H₄CCO) (LL)₂(CO)]. Reaction of [W(S₂CNEt₂)2(η²-4-Me₃C-C₆H₄CCOCOCMe₃)(CO)] (9h) with HNMe₂ gives [W(S₂CNEt₂)₂(η²-4-Me₃C-C₆H₄CCNMe₂)(CO)] (11). Reaction of 9h with PMe₃ gives [W(S₂CNEt₂)2(η²-4-Me₃CC₆H₄CCSCSNEt₂)(CO)][Me₃CO₂] (12). The reaction of 4b with PMe₃ affords [W(η²-4-Me₃CC₆H₄CCO)(S₂CNEt₂)(CO)(PMe₃)₂] (13). The (ynol ether)metal complexes [M(S₂CNEt₂)₂(CO)(η²-RCCOMe)] (6, M = Mo, R = Ph; 7, M = W, R = C₆H₄CMe₃-4) were prepared by reaction of NEt₄[M(η²-RCCO)(S₂CNR″₂)₂(CO)] with CF₃SO₃CH₃.

Original language	English
Pages (from-to)	1926-1936
Number of pages	11
Journal	Organometallics
Volume	11
Issue number	5
DOIs	https://doi.org/10.1021/om00041a027
State	Published - May 1 1992

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@article{280ec3760b8c43a6aed202bf56bd8429,

title = "Synthesis and Reactions of Ynol Ester Complexes of Molybdenum and Tungsten: Cleavage of the RCCO-C(O)R′ Bond and of the RCC-OC(O)R′ Bond of Ynol Ester Ligands",

abstract = "Reaction of the ketenyl complexes NEt4[M(η2-RCCO)(S2CNR″2)2(CO)] (3, M = Mo, R = Ph, R″ = Et; 4, M = W, R = Ph, R″ = Et (a), R = C6H4CMe3-4, R″ = Et (b), R = Ph, R″ = Me (c)) and K[W(η2-4-Me3C-C6H4CCO)(N2C6H7)2(CO)] (5) with acyl halides R′COCl (or R′COBr) affords the (ynol ester)metal complexes [M(S2CNR″)2(CO)(η2-RCCOCOR′)] (8: M = Mo, R = Ph, R′ = Ph, R″ = Et) (9: M = W, R = Ph, R′ = Me (a), Ph (b), CHCH2 (c), trans-CHCHMe (d), trans-CHCHPh (e), R″ = Et; R = C6H4CMe3-4, R′ = Me (f), CH2Ph (g), CMe3 (h), R″ = Et; R = Ph, R′ = CMe3, R″ = Me (i)) and [W(N2C6H7)2-(CO)(η2-4-Me3C-C6H4CCOCORO] (10: R = C6H4CMe3-4, R′ = CMe3 (a), CH2Ph (b), C6H4-OMe-4 (c)). Reaction of the ynol ester complexes [W(S2CNEt2)2(CO)(η2-4-Me3C-C6H4CCOCOCH2R)] (R = H (9f), Ph (9g)) with dimethylamine affords the ketenyl complex [H2NMe2] [W(η2-4-Me3C-C6H4CCO) (S2CNEt2)2(CO)]. The ynol ester complexes [W(LL)2(CO)(η2-4-Me3C-C6H4CCOCOCH2Ph)] (LL = S2CNEt2 (9g), N2C6H7 (10b)) react with NaN(SiMe3)2 to give the ketenyl complexes Na[W(η2-4-Me3C-C6H4CCO) (LL)2(CO)]. Reaction of [W(S2CNEt2)2(η2-4-Me3C-C6H4CCOCOCMe3)(CO)] (9h) with HNMe2 gives [W(S2CNEt2)2(η2-4-Me3C-C6H4CCNMe2)(CO)] (11). Reaction of 9h with PMe3 gives [W(S2CNEt2)2(η2-4-Me3CC6H4CCSCSNEt2)(CO)][Me3CO2] (12). The reaction of 4b with PMe3 affords [W(η2-4-Me3CC6H4CCO)(S2CNEt2)(CO)(PMe3)2] (13). The (ynol ether)metal complexes [M(S2CNEt2)2(CO)(η2-RCCOMe)] (6, M = Mo, R = Ph; 7, M = W, R = C6H4CMe3-4) were prepared by reaction of NEt4[M(η2-RCCO)(S2CNR″2)2(CO)] with CF3SO3CH3.",

author = "Belsky, \{Kimberly A.\} and Asaro, \{Marianna F.\} and Chen, \{Sylvia Y.\} and Andreas Mayr",

year = "1992",

month = may,

day = "1",

doi = "10.1021/om00041a027",

language = "English",

volume = "11",

pages = "1926--1936",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "5",

}

TY - JOUR

T1 - Synthesis and Reactions of Ynol Ester Complexes of Molybdenum and Tungsten

T2 - Cleavage of the RCCO-C(O)R′ Bond and of the RCC-OC(O)R′ Bond of Ynol Ester Ligands

AU - Belsky, Kimberly A.

AU - Asaro, Marianna F.

AU - Chen, Sylvia Y.

AU - Mayr, Andreas

PY - 1992/5/1

Y1 - 1992/5/1

N2 - Reaction of the ketenyl complexes NEt4[M(η2-RCCO)(S2CNR″2)2(CO)] (3, M = Mo, R = Ph, R″ = Et; 4, M = W, R = Ph, R″ = Et (a), R = C6H4CMe3-4, R″ = Et (b), R = Ph, R″ = Me (c)) and K[W(η2-4-Me3C-C6H4CCO)(N2C6H7)2(CO)] (5) with acyl halides R′COCl (or R′COBr) affords the (ynol ester)metal complexes [M(S2CNR″)2(CO)(η2-RCCOCOR′)] (8: M = Mo, R = Ph, R′ = Ph, R″ = Et) (9: M = W, R = Ph, R′ = Me (a), Ph (b), CHCH2 (c), trans-CHCHMe (d), trans-CHCHPh (e), R″ = Et; R = C6H4CMe3-4, R′ = Me (f), CH2Ph (g), CMe3 (h), R″ = Et; R = Ph, R′ = CMe3, R″ = Me (i)) and [W(N2C6H7)2-(CO)(η2-4-Me3C-C6H4CCOCORO] (10: R = C6H4CMe3-4, R′ = CMe3 (a), CH2Ph (b), C6H4-OMe-4 (c)). Reaction of the ynol ester complexes [W(S2CNEt2)2(CO)(η2-4-Me3C-C6H4CCOCOCH2R)] (R = H (9f), Ph (9g)) with dimethylamine affords the ketenyl complex [H2NMe2] [W(η2-4-Me3C-C6H4CCO) (S2CNEt2)2(CO)]. The ynol ester complexes [W(LL)2(CO)(η2-4-Me3C-C6H4CCOCOCH2Ph)] (LL = S2CNEt2 (9g), N2C6H7 (10b)) react with NaN(SiMe3)2 to give the ketenyl complexes Na[W(η2-4-Me3C-C6H4CCO) (LL)2(CO)]. Reaction of [W(S2CNEt2)2(η2-4-Me3C-C6H4CCOCOCMe3)(CO)] (9h) with HNMe2 gives [W(S2CNEt2)2(η2-4-Me3C-C6H4CCNMe2)(CO)] (11). Reaction of 9h with PMe3 gives [W(S2CNEt2)2(η2-4-Me3CC6H4CCSCSNEt2)(CO)][Me3CO2] (12). The reaction of 4b with PMe3 affords [W(η2-4-Me3CC6H4CCO)(S2CNEt2)(CO)(PMe3)2] (13). The (ynol ether)metal complexes [M(S2CNEt2)2(CO)(η2-RCCOMe)] (6, M = Mo, R = Ph; 7, M = W, R = C6H4CMe3-4) were prepared by reaction of NEt4[M(η2-RCCO)(S2CNR″2)2(CO)] with CF3SO3CH3.

AB - Reaction of the ketenyl complexes NEt4[M(η2-RCCO)(S2CNR″2)2(CO)] (3, M = Mo, R = Ph, R″ = Et; 4, M = W, R = Ph, R″ = Et (a), R = C6H4CMe3-4, R″ = Et (b), R = Ph, R″ = Me (c)) and K[W(η2-4-Me3C-C6H4CCO)(N2C6H7)2(CO)] (5) with acyl halides R′COCl (or R′COBr) affords the (ynol ester)metal complexes [M(S2CNR″)2(CO)(η2-RCCOCOR′)] (8: M = Mo, R = Ph, R′ = Ph, R″ = Et) (9: M = W, R = Ph, R′ = Me (a), Ph (b), CHCH2 (c), trans-CHCHMe (d), trans-CHCHPh (e), R″ = Et; R = C6H4CMe3-4, R′ = Me (f), CH2Ph (g), CMe3 (h), R″ = Et; R = Ph, R′ = CMe3, R″ = Me (i)) and [W(N2C6H7)2-(CO)(η2-4-Me3C-C6H4CCOCORO] (10: R = C6H4CMe3-4, R′ = CMe3 (a), CH2Ph (b), C6H4-OMe-4 (c)). Reaction of the ynol ester complexes [W(S2CNEt2)2(CO)(η2-4-Me3C-C6H4CCOCOCH2R)] (R = H (9f), Ph (9g)) with dimethylamine affords the ketenyl complex [H2NMe2] [W(η2-4-Me3C-C6H4CCO) (S2CNEt2)2(CO)]. The ynol ester complexes [W(LL)2(CO)(η2-4-Me3C-C6H4CCOCOCH2Ph)] (LL = S2CNEt2 (9g), N2C6H7 (10b)) react with NaN(SiMe3)2 to give the ketenyl complexes Na[W(η2-4-Me3C-C6H4CCO) (LL)2(CO)]. Reaction of [W(S2CNEt2)2(η2-4-Me3C-C6H4CCOCOCMe3)(CO)] (9h) with HNMe2 gives [W(S2CNEt2)2(η2-4-Me3C-C6H4CCNMe2)(CO)] (11). Reaction of 9h with PMe3 gives [W(S2CNEt2)2(η2-4-Me3CC6H4CCSCSNEt2)(CO)][Me3CO2] (12). The reaction of 4b with PMe3 affords [W(η2-4-Me3CC6H4CCO)(S2CNEt2)(CO)(PMe3)2] (13). The (ynol ether)metal complexes [M(S2CNEt2)2(CO)(η2-RCCOMe)] (6, M = Mo, R = Ph; 7, M = W, R = C6H4CMe3-4) were prepared by reaction of NEt4[M(η2-RCCO)(S2CNR″2)2(CO)] with CF3SO3CH3.

UR - https://www.scopus.com/pages/publications/0141754398

U2 - 10.1021/om00041a027

DO - 10.1021/om00041a027

M3 - Article

SN - 0276-7333

VL - 11

SP - 1926

EP - 1936

JO - Organometallics

JF - Organometallics

IS - 5

ER -

Synthesis and Reactions of Ynol Ester Complexes of Molybdenum and Tungsten: Cleavage of the RCCO-C(O)R′ Bond and of the RCC-OC(O)R′ Bond of Ynol Ester Ligands

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