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首页> 外文期刊>European journal of inorganic chemistry >Mutual Influences of Ligands as Revealed by the 2H NMR Chemical Shifts and the Angular Overlap Model Parameters:cis-[CrX2(N)4] and fac-[CrX3(N)3]-Type Complexes with Aromatic Amines
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Mutual Influences of Ligands as Revealed by the 2H NMR Chemical Shifts and the Angular Overlap Model Parameters:cis-[CrX2(N)4] and fac-[CrX3(N)3]-Type Complexes with Aromatic Amines

机译：通过2H NMR化学位移和角重叠模型显示的配体的相互影响：顺式[[CrX2（N）4]和fac- [CrX3（N）3]型与芳香胺的配合物

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A mutual influence of ligands through a pi donor-acceptor interaction is found by examining how the X co-ligands of the aromatic amine complexes cis-[CrX2([D4]bpy)2]~(n+) (bpy = 2,2'-bipyridine) and fac-[CrX3([D12]tpa)]~(n+) [tpa = tris(2-pyr-idyl)amine] affect the 2H NMR chemical shifts in connection with the Angular Overlap Model (AOM) parameterization in an analogous manner to our previous study on the solvato-chromism and solvent-dependent 2H NMR spectra of cis-[CrF2([D4]bpy)2]+ and fac-[CrF3([D12]tpa)].The ranking of the AOM parameter for monodentate and/or didentate ligands can be obtained from this co-ligand effect only from the 2H NMR shifts.The postulated relative order in the two-dimen-sional spectrochemical series is Cl~- > Br~- > O or N donors (mal~(2-) > acac~- or H2O > dmf > NCS~-) for the aromatic amine complexes,which contrasts with the order O or N donors > Cl~- > Br~- for the aliphatic amine complexes(see the preceding paper in this issue).This fact suggests that the Cr-Cl and Cr-Br sigma bonds are stronger in the soft acidic aromatic amine complexes than those in the hard acidic aliphatic amine complexes.This means they have a higher affinity for soft basic Cl~- and Br~- ligands and can be explained in terms of the hard/soft acid/base (HSAB) concept.
机译：通过检查芳族胺络合物的顺式-[CrX2（[D4] bpy）2]〜（n +）（bpy = 2,2'）的X共配体，发现通过pi供体-受体相互作用，配体之间具有相互影响。 -bipyridine）和fac- [CrX3（[D12] tpa）]〜（n +）[tpa = tris（2-pyr-idyl）amine]影响2H NMR化学位移，与Angular重叠模型（AOM）参数有关与我们先前对顺式[CrF2（[D4] bpy）2] +和fac- [CrF3（[D12] tpa）]的溶剂致变色和溶剂依赖性2H NMR谱研究类似。单齿和/或二齿配体的AOM参数只能通过2H NMR位移从该共配体效应获得。二维光谱化学序列中假定的相对顺序为Cl〜-> Br〜-> O或N芳族胺络合物的给体（mal〜（2-）> acac〜-或H2O> dmf> NCS〜-），与脂族胺络合物的O或N给体> Cl〜-> Br〜-的顺序相反（请参阅本期的前一篇论文。） Cr-Cl和Cr-Br sigma键在软酸性芳族胺络合物中比在硬酸性脂族胺络合物中强，这意味着它们对软碱性Cl〜-和Br〜-配体具有更高的亲和力，这可以解释就硬/软酸/碱（HSAB）概念而言。

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