Reactivity of Triosmium and Triruthenium Carbonyls with 2,2'-Diamino-1,1'-binaphthalene. Synthesis of C- and N-Metalated Derivatives
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- 作者：Javier A. Cabeza ; Ivá ; n da Silva ; Ignacio del Rí ; o ; Santiago Garcí ; a-Granda ; Ví ; ctor Riera ; and M. Gabriela Sá ; nchez-Vega
- 刊名：Organometallics
- 出版年：2003
- 出版时间：March 31, 2003
- 年：2003
- 卷：22
- 期：7
- 页码：1519 - 1525
- 全文大小：142K
- 年卷期：v.22,no.7(March 31, 2003)
- ISSN：1520-6041
文摘
The reaction of [Os3(MeCN)2(CO)10] with 2,2'-diamino-1,1'-binaphthalene (H2binam) affordsthe coordinatively unsaturated trinuclear derivative [Os3(
-H)(3-
2-Hbinam-N,C)(CO)9] (1),which contains a C-metalated Hbinam ligand attached to an Os atom through an NH2 groupand to the remaining two Os atoms through the metalated C atom. The unsaturation of 1is somewhat relieved by a weak interaction of a naphthalene C=C double bond with an Osatom. Curiously, treatment of [Ru3(MeCN)2(CO)10] with H2binam does not give the rutheniumanalogue of 1. The stepwise treatment of [Ru3(CO)12] with LiHbinam and [HOEt2][BF4] leadsto [Ru3(-H)(-1-Hbinam-N)(CO)10] (2), in which an N-metalated Hbinam acts as an edge-bridging amido ligand. Complex 2 reacts with bis(diphenylphosphanyl)methane (dppm) togive [Ru3(-H)2(3-2-binam-C,N)(-2-dppm-P,P)(CO)7] (3). This complex contains a doublyC- and N-metalated binam ligand attached to a Ru atom through the metalated C atom andto the remaining two Ru atoms through the metalated NH fragment. Compounds 1 and 3are the first examples of C-metalated derivatives of H2binam.
-H)(3-2-Hbinam-N,C)(CO)9] (1),which contains a C-metalated Hbinam ligand attached to an Os atom through an NH2 groupand to the remaining two Os atoms through the metalated C atom. The unsaturation of 1is somewhat relieved by a weak interaction of a naphthalene C=C double bond with an Osatom. Curiously, treatment of [Ru3(MeCN)2(CO)10] with H2binam does not give the rutheniumanalogue of 1. The stepwise treatment of [Ru3(CO)12] with LiHbinam and [HOEt2][BF4] leadsto [Ru3(-H)(-1-Hbinam-N)(CO)10] (2), in which an N-metalated Hbinam acts as an edge-bridging amido ligand. Complex 2 reacts with bis(diphenylphosphanyl)methane (dppm) togive [Ru3(-H)2(3-2-binam-C,N)(-2-dppm-P,P)(CO)7] (3). This complex contains a doublyC- and N-metalated binam ligand attached to a Ru atom through the metalated C atom andto the remaining two Ru atoms through the metalated NH fragment. Compounds 1 and 3are the first examples of C-metalated derivatives of H2binam.