The reaction between 1-boranyl-1,3,5-triaza-7-phosphaadamantane ligand N-B-PTA(BH3) and [Cp*RhCl(μ-Cl)]2 affords [Cp*Rh{N-B-PTA(BH3)}Cl2] (3) or [Cp*Rh{N-B-PTA(BH3)}2Cl]Cl (5) containing one or two P-bonded boronated PTA ligands. The hydride [Cp*Rh{N-B-PTA(BH3)}H2] (8) was also obtained by reaction of 3 with NaBH4 and alternatively by direct hydroboration of [Cp*Rh(PTA)Cl2] with excess NaBH4. Moderately slow hydrolysis of the N-boranyl rhodium complexes affords dihydrogen, H3BO3 and the corresponding PTA derivatives, including the water-soluble dihydride [Cp*Rh(PTA)H2] (9). Finally, the reaction of 8 with electron poor alkynes gives the alkene complexes [Cp*Rh{N-B-PTA(BH3)}(η2-CH2 = CHR)] (R = Ph, 10; C(O)OEt, 11) as a mixture of rotamers η2-coordinated to rhodium without affecting the N-BH3 moiety. The X-ray crystal structures of 3 and 10 were also obtained and are here discussed.

Synthesis and Reactivity of Rhodium(III) Pentamethylcyclopentadienyl Complexes of N–B PTA(BH3) : X-ray crystal structures of [Cp*RhCl2(N–B–PTA(BH3)] and [Cp*Rh{N–B–PTA(BH3)}(η2- CH2=CHPh)] / S. Bolaño, A. Albinati, J. Bravo, M. Caporali, L. Gonsalvi, L. Male, M. A. Rodríguez-Rocha, A. Rossin, M. Peruzzini. - In: JOURNAL OF ORGANOMETALLIC CHEMISTRY. - ISSN 0022-328X. - 693:14(2008), pp. 2397-2406.

Synthesis and Reactivity of Rhodium(III) Pentamethylcyclopentadienyl Complexes of N–B PTA(BH3) : X-ray crystal structures of [Cp*RhCl2(N–B–PTA(BH3)] and [Cp*Rh{N–B–PTA(BH3)}(η2- CH2=CHPh)]

A. Albinati
Secondo
;
2008

Abstract

The reaction between 1-boranyl-1,3,5-triaza-7-phosphaadamantane ligand N-B-PTA(BH3) and [Cp*RhCl(μ-Cl)]2 affords [Cp*Rh{N-B-PTA(BH3)}Cl2] (3) or [Cp*Rh{N-B-PTA(BH3)}2Cl]Cl (5) containing one or two P-bonded boronated PTA ligands. The hydride [Cp*Rh{N-B-PTA(BH3)}H2] (8) was also obtained by reaction of 3 with NaBH4 and alternatively by direct hydroboration of [Cp*Rh(PTA)Cl2] with excess NaBH4. Moderately slow hydrolysis of the N-boranyl rhodium complexes affords dihydrogen, H3BO3 and the corresponding PTA derivatives, including the water-soluble dihydride [Cp*Rh(PTA)H2] (9). Finally, the reaction of 8 with electron poor alkynes gives the alkene complexes [Cp*Rh{N-B-PTA(BH3)}(η2-CH2 = CHR)] (R = Ph, 10; C(O)OEt, 11) as a mixture of rotamers η2-coordinated to rhodium without affecting the N-BH3 moiety. The X-ray crystal structures of 3 and 10 were also obtained and are here discussed.
Settore CHIM/03 - Chimica Generale e Inorganica
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/61071
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