首个具有非氟化β-二酮结构特征的银（I）衍生物。

First structurally characterized silver(I) derivatives with nonfluorinated beta-diketones.

作者信息

Cingolani Augusto, Marchetti Fabio, Pettinari Claudio, Pettinari Riccardo, Skelton Brian W, White Allan H

机构信息

Dipartimento di Scienze Chimiche, Università degli Studi di Camerino, via S. Agostino 1, 62032 Camerino, Italy.

出版信息

Inorg Chem. 2002 Mar 11;41(5):1151-61. doi: 10.1021/ic0109391.

DOI:10.1021/ic0109391

PMID:11874350

Abstract

Synthetic, spectroscopic, and single-crystal X-ray structural studies of diverse complexes of silver(I) acylpyrazolonate salts AgQ(R') (QH = 1-phenyl-3-methyl-4-R'(C=O)-pyrazol-5-one; Q(1), R = Ph; Q(2), R' = CF(3); Q(3), R' = Me) with neutral ligands L = unidentate PR(3) (R = Ph, o-tolyl, cyclohexyl) and Hmimt (1-methyl-2-mercaptoimidazole) and bidentate dppe (Ph(2)P(CH(2))(2)PPh(2)) and trimen (N,N,N'-trimethylethylenediamine) define the donor capability of the anionic Q(R') ligand in a variety of roles. In the free ligand Q(3)H (which crystallizes in the monoclinic space group C2/c (no. 15), Z = 8, unit cell parameters a = 17.981(6) A, b = 5.0641(4) A, c = 24.271(6) A, and beta = 99.67(2)), the acidic OH group hydrogen-bonds intramolecularly to the adjacent pyrazolone oxygen, i.e., the two oxygen atoms are cis, true of the other Q(R') species structurally characterized here in their anionic complexed forms, in which they chelate the silver in the usual beta-diketonate manner, but not of the free anion, found in the array Ag(Ph(3)P)(Hmimt)(2) (triclinic space group P(-)1(no. 2), Z = 2, unit cell parameters a = 11.553(1) A, b = 11.943(1) A, c = 15.479(2) A, alpha = 74.829(2), beta = 76.094(2), and gamma = 78.185(2)), or [Ag(trimen)Q(1)] (monoclinic space group P2(1)/c (no. 14), Z = 4, unit cell parameters a = 7.982(1) A, b = 12.299(2) A, c = 21.507(3) A, and beta = 95.119(3)), which forms an infinite one-dimensional polymer string, Q(1) linking successive silver(I) atoms by coordination by way of the unsubstituted nitrogen and the pyrazolonate oxygen. In all [Ag(R(3)P)(2)(chelate-Q(1))] (R = Ph, Cy) complexes, P(2)Ag(O,O') arrays are found (R = Ph, monoclinic space group C2/c (no. 15), Z = 8, unit cell parameters a = 16.193(8) A, b = 13.859(7) A, c = 39.306(7) A, and beta = 100.02(3); R = Cy, triclinic space group P(-)1(no. 2), Z = 2, unit cell parameters a = 10.4655(9) A, b = 12.079(1) A, c = 22.804(2) A, alpha = 104.872(2), beta = 95.180(2), and gamma = 104.144(2)), also true of [Ag(Ph(3)P)(2)(O,O'-Q(2))] (triclinic space group P(-)1(no. 2), Z = 2, unit cell parameters a = 10.672(2) A, b = 10.710(2) A, c = 18.713(3) A, alpha = 87.573(2), beta = 80.972(2), and gamma = 81.734(2)), whereas [Ag(o-tol(3)P)Q(1)] (monoclinic space group P2(1)/c (no. 14), Z = 2 dimers, unit cell parameters a = 11.8221(6) A, b = 13.2601(6) A, c = 20.5141(10) A, and beta = 91.758(1)) exists as a dinuclear species containing two AgO(2)NP units where the acylpyrazolonate is coordinated in a bridging O,O'-Q-Nfashion. Silver atoms are four-coordinate in all except the Hmimt complex.

摘要

对多种酰基吡唑啉酮银（I）盐配合物AgQ(R')（QH = 1-苯基-3-甲基-4-R'(C=O)-吡唑-5-酮；Q(1)，R = Ph；Q(2)，R' = CF(3)；Q(3)，R' = Me）与中性配体L = 单齿PR(3)（R = Ph、邻甲苯基、环己基）以及Hmimt（1-甲基-2-巯基咪唑）和双齿dppe（Ph(2)P(CH(2))(2)PPh(2)）和三亚乙基四胺（N,N,N'-三甲基乙二胺）进行的合成、光谱和单晶X射线结构研究，确定了阴离子Q(R')配体在多种作用中的给体能力。在游离配体Q(3)H（其结晶于单斜晶系空间群C2/c（编号15），Z = 8，晶胞参数a = 17.981(6) Å，b = 5.0641(4) Å，c = 24.271(6) Å，β = 99.67(2)）中，酸性OH基团通过分子内氢键与相邻的吡唑啉酮氧原子相连，即两个氧原子是顺式的，这里以阴离子配合物形式结构表征的其他Q(R')物种也是如此，在这些物种中它们以通常的β-二酮形式螯合银，但在阵列Ag(Ph(3)P)(Hmimt)(2)（三斜晶系空间群P(-)1（编号2），Z = 2，晶胞参数a = 11.553(1) Å，b = 11.943(1) Å，c = 15.479(2) Å，α = 74.829(2)，β = 76.094(2)，γ = 78.185(2)）或[Ag(三亚乙基四胺)Q(1)]（单斜晶系空间群P2(1)/c（编号14），Z = 4，晶胞参数a = 7.982(1) Å，b = 12.299(2) Å，c = 21.507(3) Å，β = 95.119(3)）中发现的游离阴离子则不是这样，[Ag(三亚乙基四胺)Q(1)]形成无限一维聚合物链，Q(1)通过未取代的氮和吡唑啉酮氧原子的配位连接连续的银（I）原子。在所有[Ag(R(3)P)(2)(螯合 - Q(1))]（R = Ph、Cy）配合物中，发现了P(2)Ag(O,O')阵列（R = Ph，单斜晶系空间群C2/c（编号15），Z = 8，晶胞参数a = 16.193(8) Å，b = 13.859(7) Å，c = 39.306(7) Å，β = 100.02(3)；R = Cy，三斜晶系空间群P(-)1（编号2），Z = 2，晶胞参数a = 10.4655(9) Å，b = 12.079(1) Å，c = 22.804(2) Å，α = 104.872(2)，β = 95.180(2)，γ = 104.144(2)），[Ag(Ph(3)P)(2)(O,O'-Q(2))]（三斜晶系空间群P(-)1（编号2），Z = 2，晶胞参数a = 10.672(2) Å，b = 10.710(2) Å，c = 18.713(3) Å，α = 87.573(2)，β = 80.972(2)，γ = 81.734(2)）也是如此，而[Ag(邻甲苯基(3)P)Q(1)]（单斜晶系空间群P2(1)/c（编号14），Z = 2二聚体，晶胞参数a = 11.8221(6) Å，b = 13.2601(6) Å，c = 20.5141(10) Å，β = 91.758(1)）以双核物种形式存在，含有两个AgO(2)NP单元，其中酰基吡唑啉酮以桥连O,O'-Q-N方式配位。除Hmimt配合物外，银原子在所有配合物中均为四配位。