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Title Synthesis and structure of rhodium complexes containing a photolabile{eta}{sup 2}-carbodiimide ligand. 1,3-dipolar cycloaddition of phenyl azide to Tp{prime}Rh(CNR){sub 2} (Tp{prime}= hydrotris(3,5-dimethylpyrazolyl)borate)
Creator/Author Hessell, E.T. ; Jones, W.D. [Univ. of Rochester, NY (United States)]
Publication Date1992 Apr 01
OSTI IdentifierOSTI ID: 539387
DOE Contract NumberFG02-86ER13569
Other Number(s)ORGND7; ISSN 0276-7333
Resource TypeJournal Article
Resource RelationOrganometallics ; VOL. 11 ; ISSUE: 4 ; PBD: Apr 1992
Subject40 CHEMISTRY ; RHODIUM COMPLEXES; PHOTOLYSIS; IMIDES; BENZENE; HEXANE; LIGANDS; SYNTHESIS; X-RAY DIFFRACTION; BOND ANGLE; ORGANOMETALLIC COMPOUNDS
Description/Abstract The 1,3-dipolar cyloaddition of phenyl azide to the metal-coordinated isocyanide ligands in Tp{prime}Rh(CNR){sub 2} (Tp{prime}= hydrotris (3,5-dimethylpyrazolyl) borate, R= neopentyl, methyl, 2,6-xylyl; 1a-c) or Cp*Rh(CN-neopentyl){sub 2} (Cp*={eta}{sup 5}-1,2,3,4,5-pentamethylcyclopentadienyl; 3) in hexane produces the complexes Tp{prime}Rh(CNR)({eta}{sup 2}-PhN{double_bond}C{double_bond}NR) (R= neopentyl, methyl, 2,6-xylyl; 2a-c) and Cp*Rh(CNR)({eta}{sup 2}-PhN{double_bond}C{double_bond}N-neopentyl) (4), respectively, in high yield. The reaction is regiospecific with respect to coordination of the unsymmetrical carbodiimide ligand. Reaction of 2,4-xylyl azide with Tp{prime}Rh(CN-2-tolyl){sub 2} (1d) gives by X-ray diffraction. Complex 2d crystallizes from toluene in the triclinic space group PI with a= 10.962 (6){Angstrom}, b= 11.238 (4){Angstrom}, c= 8.691 (14){Angstrom},{alpha}= 96.95 (5){degrees},{beta}= 104.02 (5){degrees},{gamma}= 101.00 (4){degrees}, V= 2159 (5){Angstrom}{sup 3}, and Z= 2. The structure of 2d confirms the bidentate bonding of the carbodiimide and shows that the nitrogen of the carbodiimide arising from the azide is coordinated to rhodium. Photolysis of 2a in benzene produces Tp{prime}Rh(H)(Ph)(CN-neopentyl) (5) along with free PhN{double_bond}C{double_bond}N-neopentyl with a quantum yields of 1.0{+-} 0.03, whereas complex 4 is photochemically unreactive in benzene solution. The conversion of 2a to 5 can also be effected thermally, although the rate is slow at 100{degrees}C. Photolysis of 2a in the solid state results in an intramolecular reaction to give Tp{prime}Rh(H)(2-(N{double_bond}C{double_bond}N-neopentyl)C{sub 6}H{sub 4})(CN-neopentyl) (7). Addition of excess neopentyl isocyanide to 2a gives the azametallacyclobutane complex Tp{prime}RhC({double_bond}N-neopentyl)N(Ph)C({double_bond}N-neopentyl)(CN-neopentyl) (8). 51 refs., 5 figs., 4 tabs.
Country of PublicationUnited States
LanguageEnglish
Formatpp. 1496-1505 ; PL:
System Entry Date2001 May 05

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