AI Article Synopsis
- The study focuses on the preparation of Aryldiazene complexes derived from reactions between hydride species and aryldiazonium cations, highlighting various characterized complexes through IR, NMR, and X-ray crystallography techniques.
- Complexes generated, such as [Mn(CO)(3)(ArN=NH)P(2)]BF(4), demonstrate distinct properties based on substituents in the aromatic groups, with specific focus on compounds formed upon treatment with NEt(3) and subsequent protonation reactions yielding aryldiazene derivatives.
- Hydrazine complexes were also formed by reacting MnH(CO)(3)P(2) with triflic acid followed by hydrazine,
Article 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.
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Article Synopsis
- The study focuses on the synthesis of various iron hydride complexes by reacting FeCl2 with phosphites and NaBH4, resulting in complexes with bipyridine and phenanthroline ligands.
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