Reactions of a Ru(II) Phenyl Complex with Substrates that Possess C-N or C-O Multiple Bonds: C-C Bond Formation, N-H Bond Cleavage, and Decarbonylation Reactions

Description:

Article on the reactions of an Ru(II) phenyl complex with substrates that possess C-N or C-O multiple bonds and C-C bond formation, N-H bond cleavage, and decarbonylation reactions.

Creator(s):
Creation Date: February 8, 2006
Partner(s):
UNT College of Arts and Sciences
Collection(s):
UNT Scholarly Works
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Lee, John P.

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Pittard, Karl A.

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DeYonker, Nathan J.

University of North Texas

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Cundari, Thomas R., 1964-

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Gunnoe, T. Brent

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Petersen, Jeffrey L.

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Publisher Info:
Publisher Name: American Chemical Society
Place of Publication: [Washington, D.C.]
Date(s):
  • Creation: February 8, 2006
Description:

Article on the reactions of an Ru(II) phenyl complex with substrates that possess C-N or C-O multiple bonds and C-C bond formation, N-H bond cleavage, and decarbonylation reactions.

Degree:
Department: Chemistry
Note:

Reprinted with permission from Organometallics. Copyright 2006 American Chemical Society.

Note:

Abstract: The Ru(II) phenyl complex TpRu(CO)(NCMe)(Ph) (1) (Tp = hydridotris(pyrazolyl)borate) reacts with carbodiimides to yield amidinate complexes that result from C-C bond formation between the phenyl ligand and the carbodiimide carbon. Complex 1 and N-methylacetamide react to produce benzene and the amidate complex TpRu(CO){N,O-OC(Me)N(Me)} (4). The reaction of complex 1 with C≡N(tBu)}(Ph) (5), and heating a solution of PMe3 and 5 results in the observation of an equilibrium with the product of isonitrile insertion TpRu(CO){C(Ph)=NtBu}(PMe3) (6) (∆H = +9(1) kcal/mol and ∆S = +20(3)eu). The reaction of 1 with aromatic aldehydes at elevated temperatures results in C-H activation and decarbonylation of the aldehyde to produce TpRu(CO)2(Ar) (Ar = phenyl or p-tolyl) and free benzene. DFT calculations have been incorporated to study coordination and insertion reactions of ethylene, methyleneimine, formaldehyde, HC=C=NH, and C=NH into the Ru-Ph bond of the model fragment (Tab)Ru(CO)(Ph) (Tab = tris(azo)borate). In addition, the energetics of Ru-mediated decarbonylation of formaldehyde have been calculated.

Physical Description:

11 p.

Language(s):
Subject(s):
Keyword(s): phenyl complexes | substrates | multiple bonds
Source: Organometallics, 2006, Washington DC: American Chemical Society, pp. 1500-1510
Partner:
UNT College of Arts and Sciences
Collection:
UNT Scholarly Works
Identifier:
  • DOI: 10.1021/om050967h
  • ARK: ark:/67531/metadc77185
Resource Type: Article
Format: Text
Rights:
Access: Public
Citation:
Publication Title: Organometallics
Volume: 25
Page Start: 1500
Page End: 1510
Peer Reviewed: Yes