Synthesis and reactivity of early-late heterobimetallic hydrides of group 4 metals and iridium supported by mono(η5-C5Me 5) ancillary ligands: Bimetallic carbon-hydrogen bond activation

Organometallics

Volumn 27, Issue 23, 2008, Pages 6046-6049

  Oishi, Masataka ^a   Kato, Takeshi ^a   Nakagawa, Mayuko ^a   Suzuki, Hiroharu ^a  

^a TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVATION ANALYSIS; CHELATION; HAFNIUM; HYDROGEN; HYDROGEN BONDS; IRIDIUM; IRIDIUM COMPOUNDS; LIGANDS; SYNTHESIS (CHEMICAL); ZIRCONIUM; ZIRCONIUM COMPOUNDS;

ANCILLARY LIGANDS; BOND ACTIVATIONS; C-H ACTIVATIONS; GROUP 4; HETEROBIMETALLIC; HYDRIDO COMPLEXES; PENTAMETHYLCYCLOPENTADIENYL;

COMPLEXATION;

EID: 57949111258     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om800715b     Document Type: Article

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63. 3(<1%).
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69. The detailed dynamic structure of bis(pyridyl) complexes will be discussed elsewhere.
70. 6 at 100°C for 30 h gave deuterium incorporation into 4b (bridging hydride (19%), C6 (30%) and C6′ of pyridyl ligands) and free pyridine (C2, C6 (19%)).
71. n with deuterium incorporation into the methyl group of Cp*Zr (20%) and bridging hydride (60%) and with hydrogen incorporation into pyridyl ligands at C6 and C6′ (average 25%).
72. 0 earlymetal site (3 → 6) is considered to be the major mechanism. Deuterium incorporation into μ-H of 4b should be caused by oxidative addition of some low-valent intermediates to deuterated arenes: e. g. 7 → 8, 9. Additionally, we are not able to rule out the energetically less favored dihydride elimination as dihydrogen from the possible pyridyl or picolyl trihydride intermediates 8.