Display options
Cite
Albertin G, Antoniutti S, Bacchi A, et al. Aryldiazene, Aryldiazenido, and Hydrazine Complexes of Manganese. Preparation, Characterization, and X-ray Crystal Structures of [Mn(CO)(3)(4-CH(3)C(6)H(4)N=NH){PPh(OEt)(2)}(2)]BF(4) and [Mn(CO)(3)(NH(2)NH(2)){PPh(OEt)(2)}(2)]BPh(4) Derivatives. Inorg Chem. 1997;36(7):1296-1305doi: 10.1021/ic9608612.
Albertin, G., Antoniutti, S., Bacchi, A., Bordignon, E., Busatto, F., & Pelizzi, G. (1997). Aryldiazene, Aryldiazenido, and Hydrazine Complexes of Manganese. Preparation, Characterization, and X-ray Crystal Structures of [Mn(CO)(3)(4-CH(3)C(6)H(4)N=NH){PPh(OEt)(2)}(2)]BF(4) and [Mn(CO)(3)(NH(2)NH(2)){PPh(OEt)(2)}(2)]BPh(4) Derivatives. Inorganic chemistry, 36(7), 1296-1305. https://doi.org/10.1021/ic9608612
Albertin, Gabriele, et al. "Aryldiazene, Aryldiazenido, and Hydrazine Complexes of Manganese. Preparation, Characterization, and X-ray Crystal Structures of [Mn(CO)(3)(4-CH(3)C(6)H(4)N=NH){PPh(OEt)(2)}(2)]BF(4) and [Mn(CO)(3)(NH(2)NH(2)){PPh(OEt)(2)}(2)]BPh(4) Derivatives." Inorganic chemistry vol. 36,7 (1997): 1296-1305. doi: https://doi.org/10.1021/ic9608612
Albertin G, Antoniutti S, Bacchi A, Bordignon E, Busatto F, Pelizzi G. Aryldiazene, Aryldiazenido, and Hydrazine Complexes of Manganese. Preparation, Characterization, and X-ray Crystal Structures of [Mn(CO)(3)(4-CH(3)C(6)H(4)N=NH){PPh(OEt)(2)}(2)]BF(4) and [Mn(CO)(3)(NH(2)NH(2)){PPh(OEt)(2)}(2)]BPh(4) Derivatives. Inorg Chem. 1997 Mar 26;36(7):1296-1305. doi: 10.1021/ic9608612. PMID: 11669705.
Copy Download .nbib Format: NLM
Share it on

Inorg Chem. 1997 Mar 26;36(7):1296-1305. doi: 10.1021/ic9608612.

Aryldiazene, Aryldiazenido, and Hydrazine Complexes of Manganese. Preparation, Characterization, and X-ray Crystal Structures of [Mn(CO)(3)(4-CH(3)C(6)H(4)N=NH){PPh(OEt)(2)}(2)]BF(4) and [Mn(CO)(3)(NH(2)NH(2)){PPh(OEt)(2)}(2)]BPh(4) Derivatives.

Inorganic chemistry

Gabriele Albertin, Stefano Antoniutti, Alessia Bacchi, Emilio Bordignon, Fabio Busatto, Giancarlo Pelizzi

Affiliations

  1. Dipartimento di Chimica, Università di Venezia, Dorsoduro 2137, 30123 Venezia, Italy, and Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Centro CNR di Strutturistica Diffrattometrica, Università di Parma, Viale delle Scienze, 43100 Parma, Italy.

PMID: 11669705 DOI: 10.1021/ic9608612

Abstract

Aryldiazene complexes [Mn(CO)(3)(ArN=NH)P(2)]BF(4) (1, 2) and [{Mn(CO)(3)P(2)}(2)(&mgr;-HN=NArArN=NH)](BF(4))(2) (3, 4) [P = PPh(OEt)(2), PPh(2)OEt; Ar = C(6)H(5), 2-CH(3)C(6)H(4), 4-CH(3)C(6)H(4), 4-CH(3)OC(6)H(4); ArAr = 4,4'-C(6)H(4)C(6)H(4), 4,4'-(2-CH(3))C(6)H(3)C(6)H(3)(2-CH(3)), 4,4'-C(6)H(4)CH(2)C(6)H(4)] were prepared by reacting hydride species MnH(CO)(3)P(2) with the appropriate aryldiazonium cations in CH(2)Cl(2) or acetone solutions at -80 degrees C. The compounds were characterized by IR, (1)H and (31)P NMR spectra (with (15)N isotopic substitution), and a single-crystal X-ray structure determination. The complex [Mn(CO)(3)(4-CH(3)C(6)H(4)N=NH){PPh(OEt)(2)}(2)]BF(4) (1c) crystallizes in the space group C2/c with a = 31.857(5) Å, b = 11.119(2) Å, c = 22.414(3) Å, beta = 97.82(1) degrees, and Z = 8. Treatment of aryldiazene compounds 1-4 with NEt(3) gave the pentacoordinate aryldiazenido [Mn(CO)(2)(ArN(2))P(2)] (5, 6) and [{Mn(CO)(2)P(2)}(2)(&mgr;-N(2)ArArN(2))] (7, 8) [P = PPh(OEt)(2), PPh(2)OEt; Ar = C(6)H(5), 4-CH(3)C(6)H(4); ArAr = 4,4'-C(6)H(4)C(6)H(4), 4,4'-(2-CH(3))C(6)H(3)C(6)H(3)(2-CH(3))] derivatives. Protonation reactions of these aryldiazenido complexes 5-8 with HCl afforded the aryldiazene [MnCl(CO)(2)(ArN=NH)P(2)] (9) and [{MnCl(CO)(2)P(2)}(2)(&mgr;-HN=NArArN=NH)] (10) derivatives. Hydrazine complexes [Mn(CO)(3)(RNHNH(2))P(2)]BPh(4) (11, 12) [P = PPh(OEt)(2), PPh(2)OEt; R = H, CH(3), C(6)H(5), 4-NO(2)C(6)H(4)] were prepared by allowing hydride species MnH(CO)(3)P(2) to react first with triflic acid and then with the appropriate hydrazine. Their characterization by IR, (1)H and (31)P NMR spectra, and an X-ray crystal structure determination is reported. The compound [Mn(CO)(3)(NH(2)NH(2)){PPh(OEt)(2)}(2)]BPh(4) (11a) crystallizes in the space group P&onemacr; with a = 13.772(3) Å, b = 14.951(4) Å, c = 13.319(3) Å, alpha = 104.47(1) degrees, beta = 100.32(1) degrees, gamma = 111.08(1) degrees, and Z = 2. Oxidation reactions of hydrazine compounds 11 and 12 with Pb(OAc)(4) at -40 degrees C gave stable aryldiazene [Mn(CO)(3)(RN=NH)P(2)]BPh(4) and thermally unstable (upon reaching -40 degrees C) diazene [Mn(CO)(3)(HN=NH)P(2)]BPh(4) derivatives.

Publication Types