Aryldiazene, Aryldiazenido, and Hydrazine Complexes of Manganese. Preparation, Characterization, and X-ray Crystal Structures of [Mn(CO)₃(4-CH₃C₆H₄NNH){PPh(OEt)₂}₂]BF₄ and [Mn(CO)₃(NH₂NH₂){PPh(OEt)₂}₂]BPh₄ Derivatives

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.

Preparation and Reactivity of Hydrazine Complexes of Rhenium: Synthesis of 1,2‐Diazene (NH=NH) and Methyleneimine (CH2=NH) Derivatives

“…[17] The use of a mixed-ligand phosphite-carbonyl Re(CO) n P 5Ϫn fragment allows new examples of the stabilization of monodentate diazene to be achieved. It should be noted that the re- 4 , [11] but give only thermally unstable diazene complexes, which cannot be isolated.…”

“…[5] Furthermore, rhenium complexes containing NH 2 NH 2 or substituted hydrazine RNHNH 2 are very rare and include, apart from the pioneering work on [Re(NCO)-(CO) 2 (NH 2 NH 2 )P 2 ] (P ϭ tertiary phosphane), [6] only two papers, [7,8] one on [ReCp*Me 3 (NH 2 NH 2 )]CF 3 SO 3 (Cp* ϭ pentamethylcyclopentadienyl) and [Re(NH 2 NH 2 )-(CO) 3 (PPh 3 ) 2 ]CF 3 SO 3 , and another on the substitutedhydrazine complex [ReCl 2 (PPh 3 ) 2 {NNC(O)Ph}{H 2 NNHC-(S)Ph}]. [9] We have previously reported the synthesis and reactivity of mono-and bis(hydrazine) complexes of the iron triad [10] and manganese [11] of the type [MH(RNHNH 2 )P 4 ]BPh 4 , [M(RNHNH 2 ) 2 P 4 ](BPh 4 ) 2 (M ϭ Fe, Ru, Os) and [Mn(RNHNH 2 )(CO) n P 5Ϫn ]BPh 4 (P ϭ phosphites). We have now extended these studies to rhenium with the aim of pre- (CH 3 NHNH 2 )(CO) n P 5−n ]BPh 4 (n = 1, 2) with Pb(OAc) 4 at −40°C gives both [Re(CH 3 N=NH)(CO) n P 5−n ]BPh 4 and [Re(η 1 -NH=CH 2 )(CO) n P 5−n ]BPh 4 .…”

Highly effective solid phase extraction of some heavy metal ions using a cartridge filled with imprinted silica-supported N4O4 type bis(diazoimine) ligands

“…The signal at 195 ppm was for carbonyl carbons. Carbon atoms of phenolic C-OH groups signals were detected at about 130 and 129 ppm for A1 and A2 [8][9][10][11][12][13]35].…”

“…Diazonium cations are very important intermediates in the synthesis of derivatized organic and inorganic compounds because of their good electrophilic properties [3][4][5]. Even though many studies have been reported on the synthesis of mono(aryldiazonium) cations ArN þ 2 , synthesis of novel solid-supported bis(diazoimine) ligands and their solid phase extraction properties using syringe technique can be considered as a new area [6][7][8][9][10][11][12][13]. Silica-gel can be chemically activated with an active compound such as 3-aminopropyltriethoxysilane (APTES) before supporting chemicals to its surface [14][15][16][17][18].…”

Copper(I) hydrazone complexes: Synthesis, structure, DNA binding, radical scavenging and computational studies

“…In the search toward new metallic species with biological applications, copper compounds have proved to be excellent candidates [1][2][3][4][5][6][7]. The specific roles of ligands analogous to the molecules that bind to or modulate the function of biological receptors make them good candidates for drug development.…”