TY - JOUR
T1 - Cationic Rh complexes with novel spiro tetraarylpentaborate anions prepared from arylboronic acids and aryloxorhodium complexes
AU - Nishihara, Yasushi
AU - Nara, Kyoko
AU - Nishide, Yasuhiro
AU - Osakada, Kohtaro
PY - 2004/5/7
Y1 - 2004/5/7
N2 - Ar-B(OH)2 (1a: Ar = C6H4OMe-4, 1b: Ar = C6H3Me2-2,6) react immediately with Rh(OC 6H2Me-4)(PMe3)3 (2) in 5 : 1 molar ratio at room temperature to generate [Rh(PMe3)4] +[B5O6Ar4]- (3a: Ar = C6H4OMe-4, 3b: Ar = C6H3Me 2-2,6). p-Cresol (92%/Rh), anisole (80%/Rh) and H2O (364%/Rh) are formed from 1a and 2. The reaction of 1a with 2 for 24 h produces [Rh(PMe3)4]-[B5O6(OH) 4]- (4) as a yellow solid. This is attributed to hydrolytic dearylation of once formed 3a because the direct reaction of 3a with excess H2O forms 4. An equimolar reaction of 2 with phenylboroxine (PhBO)3 causes transfer of the 4-methylphenoxo ligand from rhodium to boron to produce [Rh(PMe3)4]+[B 3O3Ph3(OC6H4Me-4)] - (5). Arylboronic acids 1a and 1b react with Rh(OC6H 4Me-4)(PR3)3 (6: R = Et, 8: R = Ph.) and with Rh(OC6H4Me-4)(cod)(PR3) (11: R = iPr, 12: R = Ph) to form [Rh(PR3)4] +[B5O6Ar4]- (7a: R = Et, Ar = C6H4OMe-4, 7b: R = Et, Ar = C6H 3Me2-2,6, 9a: R = Ph, Ar = C6H 3Me2-2,6) and [Rh(cod)(PR3)(L)] +[B5O6Ar4]- (13b: R = iPr, L = acetone, Ar = C6H3Me2-2,6, 14a: R = Ph, L = PPh3, Ar = C6H4OMe-4, 14b: R = Ph, L = PPh3, Ar = C6H3Me2-2,6), respectively. Hydrolysis of 14a yields [Rh(cod)(PPh3) 2]-[B5O6(OH)4] - (15) quantitatively.
AB - Ar-B(OH)2 (1a: Ar = C6H4OMe-4, 1b: Ar = C6H3Me2-2,6) react immediately with Rh(OC 6H2Me-4)(PMe3)3 (2) in 5 : 1 molar ratio at room temperature to generate [Rh(PMe3)4] +[B5O6Ar4]- (3a: Ar = C6H4OMe-4, 3b: Ar = C6H3Me 2-2,6). p-Cresol (92%/Rh), anisole (80%/Rh) and H2O (364%/Rh) are formed from 1a and 2. The reaction of 1a with 2 for 24 h produces [Rh(PMe3)4]-[B5O6(OH) 4]- (4) as a yellow solid. This is attributed to hydrolytic dearylation of once formed 3a because the direct reaction of 3a with excess H2O forms 4. An equimolar reaction of 2 with phenylboroxine (PhBO)3 causes transfer of the 4-methylphenoxo ligand from rhodium to boron to produce [Rh(PMe3)4]+[B 3O3Ph3(OC6H4Me-4)] - (5). Arylboronic acids 1a and 1b react with Rh(OC6H 4Me-4)(PR3)3 (6: R = Et, 8: R = Ph.) and with Rh(OC6H4Me-4)(cod)(PR3) (11: R = iPr, 12: R = Ph) to form [Rh(PR3)4] +[B5O6Ar4]- (7a: R = Et, Ar = C6H4OMe-4, 7b: R = Et, Ar = C6H 3Me2-2,6, 9a: R = Ph, Ar = C6H 3Me2-2,6) and [Rh(cod)(PR3)(L)] +[B5O6Ar4]- (13b: R = iPr, L = acetone, Ar = C6H3Me2-2,6, 14a: R = Ph, L = PPh3, Ar = C6H4OMe-4, 14b: R = Ph, L = PPh3, Ar = C6H3Me2-2,6), respectively. Hydrolysis of 14a yields [Rh(cod)(PPh3) 2]-[B5O6(OH)4] - (15) quantitatively.
KW - Boron
KW - Boron-containing compounds
KW - P-containing ligands
KW - Rhodium
KW - Transition metals
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U2 - 10.1039/b315902g
DO - 10.1039/b315902g
M3 - Article
AN - SCOPUS:2642545833
SN - 1477-9226
SP - 1366
EP - 1375
JO - Dalton Transactions
JF - Dalton Transactions
IS - 9
ER -