π-Arene Complexes. 7. Heterobimetallic Complexes of Chromium and Manganese with Bridging. σ,π-Benzene and -Benzoyl Ligands

Simon Lotz; Minet Schindehutte; Petrus H. van Rooyen

doi:10.1021/om00038a021

π-Arene Complexes. 7. Heterobimetallic Complexes of Chromium and Manganese with Bridging. σ,π-Benzene and -Benzoyl Ligands

Simon Lotz, Minet Schindehutte, Petrus H. van Rooyen

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

28 Scopus citations

Abstract

The complexes [Cr{η⁶-C₆H₄XLi}(CO)₃] (X = H (a), F (b)) react with [Mn(CO)₅Br] to produce novel heterobimetallic compounds with bridging. σ,π-benzoyl ligands, (η⁶-{(CO)₅Mn}C(O)C₆H₅X)Cr(CO)₃ (1). When the reaction was executed in the presence of P(OMe)₃, complexes with a bridging benzoyl, (η⁶-{(CO)₄(P-(OMe)₃)Mn}C(O)C₆H₅)Cr(CO)₃ (1c (higher yield)), as well as a bridging phenyl ligand, (η⁶-{(CO)₄(P-(OMe)₃)Mn}C₆H₅)Cr(CO)₃ (3c), were obtained. By the refluxing of 1c in hexane, it was converted quantitatively into 3c. Using PPh₃ instead, the only product from the reaction was the unique complex (η⁶-{(CO)₄(PPh₃)Mn}C₆H₄X)Cr(CO)₃ (3a,b). Bridging benzoyl complexes [formula omitted] were obtained with [formula omitted]. The formation of [(η⁶: η⁶-XC₆H₄C(O)C₆H₄X){Cr(CO)₃}₂] (2) as a minor byproduct from the reactions which generated benzoyl dimers represents an interesting carbonyl-transfer reaction. Upon isolation of la from a dichloromethane-hexane solution, the complex crystallizes in the orthorhombic space group Pna2₁ with a = 13.084 (2) Å, b = 6.089 (2) Å, c = 40.036 (5) Å, and Z = 8 with two molecules in the asymmetric unit. The structure of 1a was determined from 5306 unique data (0 ≤ h ≤ 18, 0 ≤ k ≤ 8, 0 ≤ l ≤ 56), and refinement of 469 variables against 3521 observed (>σ(I)) data yielded R_w = 0.059. Recrystallization of the manganese-phosphorous complex 3a from a dichloromethane-hexane solution yielded crystals that were orthorhombic, Pbca, with a = 17.217 (2) Å, b = 16.407 (5) Å, c = 20.530 (10) Å, and Z = 8. The structure of 3a was determined from 8996 unique data (0 ≤ h ≤ 24, 0 ≤ k ≤ 22, 0 ≤ l ≤ 28), and refinement of 371 variables against 3465 observed (>3σ(I)) data yielded R_w = 0.035.

Original language	English (US)
Pages (from-to)	629-639
Number of pages	11
Journal	Organometallics
Volume	11
Issue number	2
DOIs	https://doi.org/10.1021/om00038a021
State	Published - Feb 1 1992
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{5adcadc775c54f959b7fafe55444f994,

title = "π-Arene Complexes. 7. Heterobimetallic Complexes of Chromium and Manganese with Bridging. σ,π-Benzene and -Benzoyl Ligands",

abstract = "The complexes [Cr{η6-C6H4XLi}(CO)3] (X = H (a), F (b)) react with [Mn(CO)5Br] to produce novel heterobimetallic compounds with bridging. σ,π-benzoyl ligands, (η6-{(CO)5Mn}C(O)C6H5X)Cr(CO)3 (1). When the reaction was executed in the presence of P(OMe)3, complexes with a bridging benzoyl, (η6-{(CO)4(P-(OMe)3)Mn}C(O)C6H5)Cr(CO)3 (1c (higher yield)), as well as a bridging phenyl ligand, (η6-{(CO)4(P-(OMe)3)Mn}C6H5)Cr(CO)3 (3c), were obtained. By the refluxing of 1c in hexane, it was converted quantitatively into 3c. Using PPh3 instead, the only product from the reaction was the unique complex (η6-{(CO)4(PPh3)Mn}C6H4X)Cr(CO)3 (3a,b). Bridging benzoyl complexes [formula omitted] were obtained with [formula omitted]. The formation of [(η6: η6-XC6H4C(O)C6H4X){Cr(CO)3}2] (2) as a minor byproduct from the reactions which generated benzoyl dimers represents an interesting carbonyl-transfer reaction. Upon isolation of la from a dichloromethane-hexane solution, the complex crystallizes in the orthorhombic space group Pna21 with a = 13.084 (2) {\AA}, b = 6.089 (2) {\AA}, c = 40.036 (5) {\AA}, and Z = 8 with two molecules in the asymmetric unit. The structure of 1a was determined from 5306 unique data (0 ≤ h ≤ 18, 0 ≤ k ≤ 8, 0 ≤ l ≤ 56), and refinement of 469 variables against 3521 observed (>σ(I)) data yielded Rw = 0.059. Recrystallization of the manganese-phosphorous complex 3a from a dichloromethane-hexane solution yielded crystals that were orthorhombic, Pbca, with a = 17.217 (2) {\AA}, b = 16.407 (5) {\AA}, c = 20.530 (10) {\AA}, and Z = 8. The structure of 3a was determined from 8996 unique data (0 ≤ h ≤ 24, 0 ≤ k ≤ 22, 0 ≤ l ≤ 28), and refinement of 371 variables against 3465 observed (>3σ(I)) data yielded Rw = 0.035.",

author = "Simon Lotz and Minet Schindehutte and {van Rooyen}, {Petrus H.}",

year = "1992",

month = feb,

day = "1",

doi = "10.1021/om00038a021",

language = "English (US)",

volume = "11",

pages = "629--639",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "2",

}

TY - JOUR

T1 - π-Arene Complexes. 7. Heterobimetallic Complexes of Chromium and Manganese with Bridging. σ,π-Benzene and -Benzoyl Ligands

AU - Lotz, Simon

AU - Schindehutte, Minet

AU - van Rooyen, Petrus H.

PY - 1992/2/1

Y1 - 1992/2/1

N2 - The complexes [Cr{η6-C6H4XLi}(CO)3] (X = H (a), F (b)) react with [Mn(CO)5Br] to produce novel heterobimetallic compounds with bridging. σ,π-benzoyl ligands, (η6-{(CO)5Mn}C(O)C6H5X)Cr(CO)3 (1). When the reaction was executed in the presence of P(OMe)3, complexes with a bridging benzoyl, (η6-{(CO)4(P-(OMe)3)Mn}C(O)C6H5)Cr(CO)3 (1c (higher yield)), as well as a bridging phenyl ligand, (η6-{(CO)4(P-(OMe)3)Mn}C6H5)Cr(CO)3 (3c), were obtained. By the refluxing of 1c in hexane, it was converted quantitatively into 3c. Using PPh3 instead, the only product from the reaction was the unique complex (η6-{(CO)4(PPh3)Mn}C6H4X)Cr(CO)3 (3a,b). Bridging benzoyl complexes [formula omitted] were obtained with [formula omitted]. The formation of [(η6: η6-XC6H4C(O)C6H4X){Cr(CO)3}2] (2) as a minor byproduct from the reactions which generated benzoyl dimers represents an interesting carbonyl-transfer reaction. Upon isolation of la from a dichloromethane-hexane solution, the complex crystallizes in the orthorhombic space group Pna21 with a = 13.084 (2) Å, b = 6.089 (2) Å, c = 40.036 (5) Å, and Z = 8 with two molecules in the asymmetric unit. The structure of 1a was determined from 5306 unique data (0 ≤ h ≤ 18, 0 ≤ k ≤ 8, 0 ≤ l ≤ 56), and refinement of 469 variables against 3521 observed (>σ(I)) data yielded Rw = 0.059. Recrystallization of the manganese-phosphorous complex 3a from a dichloromethane-hexane solution yielded crystals that were orthorhombic, Pbca, with a = 17.217 (2) Å, b = 16.407 (5) Å, c = 20.530 (10) Å, and Z = 8. The structure of 3a was determined from 8996 unique data (0 ≤ h ≤ 24, 0 ≤ k ≤ 22, 0 ≤ l ≤ 28), and refinement of 371 variables against 3465 observed (>3σ(I)) data yielded Rw = 0.035.

AB - The complexes [Cr{η6-C6H4XLi}(CO)3] (X = H (a), F (b)) react with [Mn(CO)5Br] to produce novel heterobimetallic compounds with bridging. σ,π-benzoyl ligands, (η6-{(CO)5Mn}C(O)C6H5X)Cr(CO)3 (1). When the reaction was executed in the presence of P(OMe)3, complexes with a bridging benzoyl, (η6-{(CO)4(P-(OMe)3)Mn}C(O)C6H5)Cr(CO)3 (1c (higher yield)), as well as a bridging phenyl ligand, (η6-{(CO)4(P-(OMe)3)Mn}C6H5)Cr(CO)3 (3c), were obtained. By the refluxing of 1c in hexane, it was converted quantitatively into 3c. Using PPh3 instead, the only product from the reaction was the unique complex (η6-{(CO)4(PPh3)Mn}C6H4X)Cr(CO)3 (3a,b). Bridging benzoyl complexes [formula omitted] were obtained with [formula omitted]. The formation of [(η6: η6-XC6H4C(O)C6H4X){Cr(CO)3}2] (2) as a minor byproduct from the reactions which generated benzoyl dimers represents an interesting carbonyl-transfer reaction. Upon isolation of la from a dichloromethane-hexane solution, the complex crystallizes in the orthorhombic space group Pna21 with a = 13.084 (2) Å, b = 6.089 (2) Å, c = 40.036 (5) Å, and Z = 8 with two molecules in the asymmetric unit. The structure of 1a was determined from 5306 unique data (0 ≤ h ≤ 18, 0 ≤ k ≤ 8, 0 ≤ l ≤ 56), and refinement of 469 variables against 3521 observed (>σ(I)) data yielded Rw = 0.059. Recrystallization of the manganese-phosphorous complex 3a from a dichloromethane-hexane solution yielded crystals that were orthorhombic, Pbca, with a = 17.217 (2) Å, b = 16.407 (5) Å, c = 20.530 (10) Å, and Z = 8. The structure of 3a was determined from 8996 unique data (0 ≤ h ≤ 24, 0 ≤ k ≤ 22, 0 ≤ l ≤ 28), and refinement of 371 variables against 3465 observed (>3σ(I)) data yielded Rw = 0.035.

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DO - 10.1021/om00038a021

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JO - Organometallics

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IS - 2

ER -

π-Arene Complexes. 7. Heterobimetallic Complexes of Chromium and Manganese with Bridging. σ,π-Benzene and -Benzoyl Ligands

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