Globular molecular platinum carbonyl nanoclusters: Synthesis and molecular structures of the [Pt26(CO)32]- and [Pt14+x(CO)18+x]4- anions and their comparison to related platinum "browns"

被引：10

作者：

Cattabriga, Enrico ^{[1
]}

Ciabatti, Iacopo ^{[1
]}

Femoni, Cristina ^{[1
]}

Iapalucci, Maria Carmela ^{[1
]}

Longoni, Giuliano ^{[1
]}

Zacchini, Stefano ^{[1
]}

机构：

[1] Univ Bologna, Dipartimento Chim Ind Toso Montanari, Viale Risorgimento 4, I-40136 Bologna, Italy

来源：

INORGANICA CHIMICA ACTA | 2018年 / 470卷

关键词：

Cluster compound; Carbonyl ligand; Platinum; Molecular structure; Nanocluster; POTENTIAL-DEPENDENT SPECTRA; CORE-SHELL NANOPARTICLES; OXYGEN REDUCTION; TEMPLATING FABRICATION; TERTIARY PHOSPHINES; METHANOL OXIDATION; METAL NANOCLUSTERS; OPTICAL-PROPERTIES; CATALYTIC-ACTIVITY; GOLD NANOCLUSTERS;

D O I：

10.1016/j.ica.2017.04.045

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The thermal decomposition of [Pt-3n(CO)(6n)](2) (n = 2-10) Chini clusters results in the formation of globular molecular platinum carbonyl clusters, whose nature depends of the nuclearity of the parent cluster as well as the counter-ion and solvent employed. Among these, the new [Pt14+x(CO)(18+x)](4) (x = 0,1) and [Pt-44(CO)(45)](n) , as well as the previously reported [Pt-15(CO)(19)](4) , [Pt-19(CO)(22)](4) , [Pt-24(CO)(30)](2) , [Pt-26(CO)(32)](2) , [Pt-33(CO)(38)](2) and [Pt-38(CO)(44)](2) have been identified. Oxidation of [Pt14+x(CO)(18+x)](4) (x = 0,1) with HBF4.Et2O affords [Pt-26(CO)(32)](2) , which is further oxidized to the related [Pt-26(CO)(32)] mono-anion. Oxidation of [Pt-19(CO)(22)](4) , under similar conditions, affords the unstable [Pt-19(CO)(22)](2) di-anion, that rearranges during crystallization into the new [Pt-36(CO)(44)](2) . Conversely, the reduction of [Pt-19(CO)(22)](4) with Na/naphthalene results in the [Pt-19(CO)(22)](5) penta-anion which, after work-up, is transformed into the new [Pt-23(CO)(27)](2) . The new clusters [Pt14+x(CO)(18+x)](4) (x = 0,1) and [Pt-26(CO)(32)] have been fully characterized by means of single crystal X-ray diffractometry as their [NEt4](4)[Pt14+x(CO)(18+x)].MeCN (x = 0.18) and [NEt4][Pt-26(CO)(32)].2.12thf.0.38C(6)H(14) salts. Conversely, in the case of the new [Pt-23(CO)(27)](2) , [Pt-36(CO)(44)](2) and [Pt-44(CO)(45)] (n) , due to the poor quality of their crystals, only a partial structural determination has been possible. [Pt14+x(CO)(18+x)](4) (x = 0,1) displays a distorted bcc structure, [Pt-26(CO)(32)] and [Pt-23(CO)(27)](2) adopt hcp structures, [Pt-36(CO)(44)](2) presents a distorted ccp metal core, whereas [Pt-44(CO)(45)](n) possesses a twinned hcp/ccp ABCBA structure. The structures of the metal cores of these clusters is compared to previously reported globular platinum carbonyl nanoclusters ("platinum browns"). (c) 2017 Elsevier B.V. All rights reserved.

引用

页码：238 / 249

页数：12

共 103 条

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