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Transformations of Group 7 Carbonyl Complexes: Possible Intermediates in a Homogeneous Syngas Conversion Scheme.

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Title: Transformations of Group 7 Carbonyl Complexes: Possible Intermediates in a Homogeneous Syngas Conversion Scheme.
Authors: Paul R. Elowe1, Nathan M. West1, Jay A. Labinger1, John E. Bercaw1
Source: Organometallics. Nov2009, Vol. 28 Issue 21, p6218-6227. 10p.
Subjects: Metal complexes, Carbonyl compounds, Intermediates (Chemistry), Chemical bonds, Synthesis gas, Metal catalysts, Boranes, Organomanganese compounds
Abstract: A variety of C−H and C−C bond forming reactions of group 7 carbonyl complexes have been studied as potential steps in a homogeneously catalyzed conversion of syngas to C2犉ꦢ. The metal formyl complexes M(CO)3(PPh3)2(CHO) (M = Mn, Re) are substantially stabilized by coordination of boranes BX3(X = F, C6F5) in the form of novel boroxycarbene complexes M(CO)3(PPh3)2(CHOBX3), but these boron-stabilized carbenes do not react with hydride sources to undergo further reduction to metal alkyls. The related manganese methoxycarbene cations [Mn(CO)5−x(PPh3)x(CHOMe)](x= 1 or 2), obtained by methylation of the formyls, do react with hydrides to form methoxymethyl complexes, which undergo further migratory insertion under an atmosphere of CO. The resulting acyls, cis- and trans-Mn(PPh3)(CO)4(C(O)CH2OMe), can be alkylated to form the cationic carbene complex [Mn(PPh3)(CO)4(C(OR)CH2OMe)], which undergoes a 1,2 hydride shift to form 1,2-dialkoxyethylene, which is displaced from the metal, releasing triflate or diethyl ether adducts of [Mn(PPh3)(CO)4]. The acyl can also be protonated with HOTf to form a hydroxycarbene complex, which rearranges to Mn(PPh3)(CO)4(CH2COOMe) and is protonolyzed to yield methyl acetate and [Mn(PPh3)(CO)4]; addition of L (L = PPh3, CO) to the manganese cation regenerates [Mn(PPh3)(CO)4(L)]. Since the original formyl complex can be obtained by the reaction of [Mn(PPh3)(CO)5]숫 [PtH(dmpe)2], which in turn can be generated from H2, this set of transformations amounts to a stoichiometric cycle for selectively converting H2and CO into a C2compound under mild conditions. [ABSTRACT FROM AUTHOR]
Copyright of Organometallics is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Data: Transformations of Group 7 Carbonyl Complexes: Possible Intermediates in a Homogeneous Syngas Conversion Scheme.
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  Data: <searchLink fieldCode="AR" term="%22Paul+R%2E+Elowe%22">Paul R. Elowe</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Nathan+M%2E+West%22">Nathan M. West</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Jay+A%2E+Labinger%22">Jay A. Labinger</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22John+E%2E+Bercaw%22">John E. Bercaw</searchLink><relatesTo>1</relatesTo>
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  Data: <searchLink fieldCode="JN" term="%22Organometallics%22">Organometallics</searchLink>. Nov2009, Vol. 28 Issue 21, p6218-6227. 10p.
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  Data: A variety of C−H and C−C bond forming reactions of group 7 carbonyl complexes have been studied as potential steps in a homogeneously catalyzed conversion of syngas to C2犉ꦢ. The metal formyl complexes M(CO)3(PPh3)2(CHO) (M = Mn, Re) are substantially stabilized by coordination of boranes BX3(X = F, C6F5) in the form of novel boroxycarbene complexes M(CO)3(PPh3)2(CHOBX3), but these boron-stabilized carbenes do not react with hydride sources to undergo further reduction to metal alkyls. The related manganese methoxycarbene cations [Mn(CO)5−x(PPh3)x(CHOMe)](x= 1 or 2), obtained by methylation of the formyls, do react with hydrides to form methoxymethyl complexes, which undergo further migratory insertion under an atmosphere of CO. The resulting acyls, cis- and trans-Mn(PPh3)(CO)4(C(O)CH2OMe), can be alkylated to form the cationic carbene complex [Mn(PPh3)(CO)4(C(OR)CH2OMe)], which undergoes a 1,2 hydride shift to form 1,2-dialkoxyethylene, which is displaced from the metal, releasing triflate or diethyl ether adducts of [Mn(PPh3)(CO)4]. The acyl can also be protonated with HOTf to form a hydroxycarbene complex, which rearranges to Mn(PPh3)(CO)4(CH2COOMe) and is protonolyzed to yield methyl acetate and [Mn(PPh3)(CO)4]; addition of L (L = PPh3, CO) to the manganese cation regenerates [Mn(PPh3)(CO)4(L)]. Since the original formyl complex can be obtained by the reaction of [Mn(PPh3)(CO)5]숫 [PtH(dmpe)2], which in turn can be generated from H2, this set of transformations amounts to a stoichiometric cycle for selectively converting H2and CO into a C2compound under mild conditions. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
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  Data: <i>Copyright of Organometallics is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1021/om900804j
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      – Code: eng
        Text: English
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        PageCount: 10
        StartPage: 6218
    Subjects:
      – SubjectFull: Metal complexes
        Type: general
      – SubjectFull: Carbonyl compounds
        Type: general
      – SubjectFull: Intermediates (Chemistry)
        Type: general
      – SubjectFull: Chemical bonds
        Type: general
      – SubjectFull: Synthesis gas
        Type: general
      – SubjectFull: Metal catalysts
        Type: general
      – SubjectFull: Boranes
        Type: general
      – SubjectFull: Organomanganese compounds
        Type: general
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      – TitleFull: Transformations of Group 7 Carbonyl Complexes: Possible Intermediates in a Homogeneous Syngas Conversion Scheme.
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            NameFull: Jay A. Labinger
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              Text: Nov2009
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              Y: 2009
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