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首页> 外文期刊>Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics >SYNTHESIS AND CHARACTERIZATION OF SIX-COORDINATE NITRIDO COMPLEXES OF VANADIUM(V), CHROMIUM(V), AND MANGANESE(V) - ISOLATION OF A DINUCLEAR, MIXED-VALENT MU-NITRIDO CHROMIUM(III)/CHROMIUM(V) SPECIES
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SYNTHESIS AND CHARACTERIZATION OF SIX-COORDINATE NITRIDO COMPLEXES OF VANADIUM(V), CHROMIUM(V), AND MANGANESE(V) - ISOLATION OF A DINUCLEAR, MIXED-VALENT MU-NITRIDO CHROMIUM(III)/CHROMIUM(V) SPECIES

机译:钒(V),铬(V)和锰(V)的六配位亚硝酸根络合物的合成和表征

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Photolysis of a series of octahedral monoazido complexes of the type [LM(III)(didentate ligand)(N-3)](n+)X(n) of vanadium(III), chromium(III), and manganese(III) in the solid state or in solution yields quantitatively the corresponding six-coordinate nitrido complexes [LM(V)(didentate ligand)(N)](n+)X(n) and 1 equiv of dinitrogen. L represents the macrocycle 1,4,7-triazacyclononane or its N-methylated derivative (L'), the didentate ligands are pentane-2,4-dionate (acac), 2,2,6,6-tetramethylheptane-3,5-dionate (tacac), picolinate (pie), phenanthroline (phen), and oxalate (ox), and X(-) represents perchlorate or hexafluorophosphate. The following nitrido complexes were prepared: [LV(V)(N)(acac)](ClO4) (6), [LCr(V)(N)(acac)](ClO4) (13), [LCr(V)(N)(tacac)](ClO4) (14), [LCr(V)(N)(pic)](ClO4) (15), [LCr(V)(N)(phen)](ClO4)(2) (16), [LCr(V)(N)(ox)] (19), [L'Mn-V(N)(acac)]PF6 (21). Photolysis of [LCr(III)(N-3)(ox)] (17) in the solid state produces the mu-nitrido-bridged mixed-valent species [L(2)Cr(2)(ox)(2)(mu-N)](N-3) (18). The structures of the precursor complex [L'Mn(acac)(N-3)]BPh(4) (20), of 13, and of [L'Mn-V(N)(acac)]BPh(4) (21) have been determined by X-ray crystallography. Complex 13 crystallizes in the orthorhombic space group Pnma, with cell constants a = 27.187(5) Angstrom, b = 9.228(2) Angstrom, c = 7.070(1) Angstrom, V = 1773.7(6) Angstrom(3) and Z = 4; complex 20 crystallizes in the triclinic space group P (1) over bar with a = 14.769(5) Angstrom, b = 16.83(1) Angstrom, c = 16.96(1) Angstrom, alpha = 108.19(5)degrees, beta = 105.06(4)degrees, gamma = 99.78(4)degrees, V = 3719(2) Angstrom(3), and Z = 4; and complex 21 crystallizes in the monoclinic space group P2(1) with a 10.443(3) Angstrom, b = 16.035(4) Angstrom, c = 21.463(5) Angstrom, beta = 95.76(1)degrees, V = 3575.9(14) Angstrom(3), and Z = 4. The Cr-V=N and Mn-V=N distances are short at 1.575(9) and 1.518(4) Angstrom, respectively, and indicate a metal-to-nitrogen triple bond. [References: 42]
机译:钒(III),铬(III)和锰(III)的[LM(III)(二配体)(N-3)(n +)X(n)类型的一系列八面体单叠氮化物络合物的光解固态或溶液中可定量产生相应的六配位亚硝基络合物[LM(V)(二配体)(N)](n +)X(n)和1当量的二氮。 L代表大环1,4,7-三氮杂环壬烷或其N-甲基化衍生物(L'),二齿配位体为2,4-戊二酸戊烷(acac),2,2,6,6-四甲基庚烷-3,5 -二酸酯(tacac),吡啶甲酸酯(pie),菲咯啉(phen)和草酸酯(ox),X(-)代表高氯酸酯或六氟磷酸酯。制备了以下亚硝基配合物:[LV(V)(N)(acac)](ClO4)(6),[LCr(V)(N)(acac)](ClO4)(13),[LCr(V) (N)(tacac)](ClO4)(14),[LCr(V)(N)(pic)](ClO4)(15),[LCr(V)(N)(phen)](ClO4)(2 )(16),[LCr(V)(N)(ox)](19),[L'Mn-V(N)(acac)] PF6(21)。 [LCr(III)(N-3)(ox)](17)在固态下的光解产生mu-nitrido-bridged混合价种[L(2)Cr(2)(ox)(2)( mu-N)](N-3)(18)。前体络合物[L'Mn(acac)(N-3)] BPh(4)的结构(13)和[L'Mn-V(N)(acac)] BPh(4)的结构( 21)已通过X射线晶体学测定。络合物13在正交空间群Pnma中结晶,单元常数a = 27.187(5)埃,b = 9.228(2)埃,c = 7.070(1)埃,V = 1773.7(6)埃(3)和Z = 4;络合物20在三边形空间群P(1)中结晶成a = 14.769(5)埃,b = 16.83(1)埃,c = 16.96(1)埃,alpha = 108.19(5)度,beta = 105.06 (4)度,伽玛= 99.78(4)度,V = 3719(2)埃(3),Z = 4;且复合物21在单斜空间群P2(1)/ n中以10.443(3)埃,b = 16.035(4)埃,c = 21.463(5)埃,β= 95.76(1)度,V = 3575.9结晶(14)埃(3),Z =4。Cr-V = N和Mn-V = N距离分别短于1.575(9)和1.518(4)埃,表示金属与氮的距离三键。 [参考:42]

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