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Nortricyclyl‐ and Norbornenyl‐Acylrhodium Complexes from the Reaction of Norbornadiene Rhodium( I ) Complexes with o ‐(Diphenylphosphanyl)benzaldehyde
Author(s) -
El Mail Rachad,
Garralda María Angeles,
Hernández Ricardo,
Ibarlucea Lourdes,
Pinilla Elena,
Torres María Rosario,
Zarandona Malkoa
Publication year - 2005
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200400935
Subject(s) - chemistry , norbornadiene , rhodium , denticity , medicinal chemistry , pyridine , benzaldehyde , nuclear magnetic resonance spectroscopy , stereochemistry , benzene , crystal structure , catalysis , crystallography , organic chemistry
[{Rh(Nbd)Cl} 2 ] (Nbd = norbornadiene) reacts with o ‐(diphenylphosphane)benzaldehyde in benzene solution to give the rhodium( III ) complex [Rh(Cl)(C 7 H 9 ){ o ‐PPh 2 (C 6 H 4 CO)}] n ( 1 ), where C 7 H 9 is a nortricyclyl (Ntyl) group. Complex 1 reacts with various bidentate N‐donors, such as biacetyldihydrazone, 2,2'‐bipyridine, 8‐aminoquinoline, 2‐(aminomethyl)pyridine, or pyridine, to afford nortricyclyl [Rh(Cl){ o ‐PPh 2 (C 6 H 4 CO)}(Ntyl)(NN)] complexes. The presence of the nortricyclyl group and the structure of the complexes have been confirmed by NMR spectroscopy and, in one case, by single‐crystal X‐ray diffraction. Nortricyclyl complexes containing bidentate N‐donors are also formed by the reaction in benzene of PPh 2 ( o ‐C 6 H 4 CHO) with the corresponding [Rh(Cl)(Nbd)(NN)] compounds prepared “in situ”. [Rh(Cl)(Nbd)(bipy)] prepared “in situ” reacts with PPh 2 ( o ‐C 6 H 4 CHO) in methanol to give the complex [Rh(Cl){ o ‐PPh 2 (C 6 H 4 CO)}(C 7 H 9 )(bipy)], where C 7 H 9 is a norbornenyl (Nbyl) group. This compound has been fully characterized by NMR spectroscopy. A proposal for the selective production of the norbornenyl and the nortricyclyl derivatives is presented. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)