Synthesis and electrochemistry of polymeric complexes with cationic manganese carbonyl fragments coordinated to polyphosphazenes through nitrile ligands

• Published in: Journal of organometallic chemistry 1995-11, Vol.503 (1), p.59-67
• Main Authors: Carriedo, Gabino A., Fernández-Catuxo, Lucía, García Alonso, Francisco J., Gómez-Elipe, Paloma
• Format: Article
• Language: English
• Subjects: Carbonyls; Cationic; Complexes; Manganese; Phosphazene; Polymeric
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/0022-328X(95)05540-6

The cyclotriphosphazenes N 3P 3(OC 6H 4R-4) 5(OC 6H 4CN-4), R  H ( 1a) or tBu( 1b), reacted with trans-[ MnBr( CO) 2( dppm) [ P( OPh) 3] and TIPF 6 in dichloromethane to give the monocationic complexes [{N 3P 3(OC 6H 4R-4) 5(OC 6H 4CN)}Mn(CO) 2(dppm) {P(OPh) 3}][PF 6], R  H ( 2a) or tBu( 2b). Similarly the hexafunctionalized cyclotriphosphazene N 3P 3(OC 6H 4CN-4) 6 ( 4) reacted in CH 2Cl 2 with trans-[ MnBr( CO) 2( dppm) { P( OPh) 3}] in the presence of TIPF 6, and with fac-[Mn(OClO 3)(CO) 3(PP)] (PP = dppm or dppe), to give the hexacationic complexes [N 3P 3{(OC 6H 4CN)Mn(CO) 2(dppm)[P(OPh) 3]} 6][PF 6] 6 ( 5a), [N 3P 3{(OC 6H 4CN)Mn(CO) 3(PP)} 6]-(ClO 4) 6 (PP = dppm, 6a, or dppe, 6b). In all cases, the changes in the 31P NMR chemical shifts for the phosphorus of the phosphazene ring, the molar conductivities in acetone solution and the cyclic voltammograms in CH 2Cl 2 of the complexes containing the trans- Mn( CO) 2( dppm)[ P( OPh) 3] moiety showed a good correlation with the number of metal-carbonyl units bonded to the phosphazene in the mono- and hexa-cationic complexes. Similarly, the nitrile-containingphosphazene polymers {NP(OC 6H 5) 2− x (OC 6H 4CN-4) x } n ( x = 0.06, 7 a; x = 0.28, 7 b), reacted with the corresponding manganese carbonyls to give the complexes {NP(OC 6H 5) 2− x {[OC 6H 4CNMn(CO) 2(dppm){P(OPh) 3} (PF 6)] x } n ( x = 0.06, 8 a; x = 0.28, 8 b) and {NP(OC 6H 5) 1.94[OC 6H 4CNMn(CO) 3(dppe)(ClO) 4)] 0.06} n ( 9). The cyclic voltammogram of the polymers 8a and 8b in CH 2Cl 2 showed a very extended oxidation wave with large θE p .