Bortoluzzi Marco, Cesari Cristiana, Ciabatti Iacopo, Femoni Cristina, Iapalucci Maria Carmela, Zacchini Stefano
Dipartimento di Scienze Molecolari e Nanosistemi, Ca' Foscari University of Venice , Via Torino 155, 30175 Mestre, Venice, Italy.
Dipartimento di Chimica Industriale "Toso Montanari″, University of Bologna , Viale Risorgimento 4, I-40136 Bologna Italy.
Inorg Chem. 2017 Jun 5;56(11):6532-6544. doi: 10.1021/acs.inorgchem.7b00665. Epub 2017 May 10.
The reactions of anionic platinum carbonyl Chini clusters [Pt(CO)] [n = 2 (1), 3 (2), 4 (3)] with Ag(IPr)Cl [IPr = CNH(CHPr)] afford the neutral acid-base Lewis adducts [Pt(CO)(AgIPr)] (4) and [Pt(CO)(AgIPr)] (5). These are thermally transformed into the homometallic heteroleptic neutral cluster [Pt(CO)(IPr)] (6). Alternatively, 6 can be obtained from the reactions of 1-3 with an excess of the free IPr carbene ligand. The formation of 6 is sometimes accompanied by trace amounts of [Pt(CO)(IPr)] (7). The reaction of 6 with free IPr affords the closely related [Pt(CO)(IPr)] (8) heteroleptic cluster by substitution of the unique terminal CO ligand with a third IPr ligand. The reactions of 1-3 with Ag(IMes)Cl [IMes = CNH(CHMe)] proceed differently from those involving Ag(IPr)Cl. Indeed, the only product isolated after workup is the bimetallic tetranuclear cluster [Pt(CO)(IMes)(AgCl)] (9). 9 slowly reacts under a CO atmosphere, resulting in the pentanuclear [Pt(CO)(IMes)] (10) complex. All of the new clusters 4-10 have been spectroscopically characterized and their molecular structures determined by X-ray crystallography. 4 and 5 retain the original trigonal-prismatic structures of the parent anionic Chini clusters, which are capped by two [Ag(IPr)] moieties. Conversely, 6-9 are based on a Pt triangular core decorated by CO and N-heterocyclic carbene ligands as well as Pt(CO) (in the case of 7) and AgCl (9) moieties. 10 displays an edge-bridged tetrahedral geometry.
阴离子型羰基铂奇尼簇合物[Pt(CO)]（n = 2 (1)、3 (2)、4 (3)）与Ag(IPr)Cl [IPr = CNH(CHPr)]反应生成中性酸碱路易斯加合物[Pt(CO)(AgIPr)]（4）和[Pt(CO)(AgIPr)]（5）。这些加合物经热转化为同金属杂配中性簇合物[Pt(CO)(IPr)]（6）。或者，6可由1 - 3与过量的游离IPr卡宾配体反应制得。6的形成有时伴随着痕量的[Pt(CO)(IPr)]（7）。6与游离IPr反应，通过用第三个IPr配体取代独特的末端CO配体，得到密切相关的[Pt(CO)(IPr)]（8）杂配簇合物。1 - 3与Ag(IMes)Cl [IMes = CNH(CHMe)]的反应与涉及Ag(IPr)Cl的反应不同。实际上，后处理后分离得到的唯一产物是双金属四核簇合物[Pt(CO)(IMes)(AgCl)]（9）。9在CO气氛下缓慢反应，生成五核[Pt(CO)(IMes)]（10）配合物。所有新簇合物4 - 10均已通过光谱表征，并通过X射线晶体学确定了它们的分子结构。4和5保留了母体阴离子奇尼簇合物的原始三棱柱结构，由两个[Ag(IPr)]部分封端。相反，6 - 9基于由CO和N - 杂环卡宾配体以及Pt(CO)（对于7）和AgCl（9）部分修饰的Pt三角形核心。10呈现出边桥连四面体几何结构。
