Pt 2 Os 3(CO)10(PBu t 3)(PBu t 2 CMe 2 CH 2)(µ-H)(1)和Pt 2 Os 3(CO)9(PBu t 3)(µ- PBU吨2)(μ-H)(μ 3 -CCMe 2)(2,从O的反应获得)3(CO)12与铂(PBU吨3)2在97℃。化合物2是新的,由具有桥接PBU 5个金属原子的四方锥簇吨2配体,桥接氢基配体和一个桥连三重配体dimethylvinylideneC═CMe 2通过的三-变换形成叔丁基膦的配体。在125°C下将化合物1转化为2,然后将化合物2转化为两种新化合物,即PtOs 3(CO)7(PBu t 3)(µ-PBu t 2)(µ 4 -CHCMeCH)(3)和Pt 4 Os 3(CO)12(µ-PBut 2)2(4),在174°C下。化合物3在四个金属原子的蝶形簇中包含桥连的PBu t 2配体和四重桥连的CHCMeCH配体。化合物4包
从Os 3(CO)10(NCMe)2与Pt(PBu t 3)2的反应获得电子不饱和簇络合物Os 3 Pt 2(CO)10(PBu t 3)2(10)。三副产品:PtOs 3(CO)10(PBu t 2)CMe 2 CH 2(μ-H)(13),Os 3(CO)10(PBu t 3)2(14)和Pt 2 Os 3(CO)10(PBu t 3)(PBu t 2)CMe 2 CH 2(μ-H)(15)也得到。10个中的三个原子位于三角双锥的赤道平面内。铂原子占据顶端位置。加热时,通过在与之配位的铂原子上的一个PBu t 3配体之一的甲基之一的金属化,将化合物10转化为15。然后,铂原子转移到Os 3的边缘通过切割其Pt-Os键之一而形成三角形。化合物13还包含连接到四面体PtO 3簇的铂原子上的金属化的PBu t 3配体。化合物10在0°C下与氢反应生成二氢和四氢化合物Os 3 Pt 2(CO)10(PBu
Platinum−Osmium Cluster Complexes from the Addition of Pt(PBu<sup>t</sup><sub>3</sub>) Groups to Os<sub>3</sub>(CO)<sub>12</sub>
作者:Richard D. Adams、Burjor Captain、Lei Zhu
DOI:10.1021/ic0515507
日期:2006.1.1
Three new compounds, PtOs3(CO)(12)(PBu3t) (10), Pt2Os3(CO)(12)(PBu3t)(2) (11), and Pt3Os3(CO)(12)(PBu3t)(3) (12), have been obtained from the reaction of Pt(PBu3t)(2) with Os-3(CO)(12) (9). The products were formed by the sequential addition of 1-3 Pt(PBu3t) groups to the three Os-Os bonds of the metal cluster of Os-3(CO)(12). In solution, compounds 10-12 interconvert among themselves by intermolecular exchange of the Pt(PBu3t) groups. When 11 is treated with PPh3, the mono- and bis(PPh3) derivatives of 9, Os-3(CO)(11)(PPh3) and Os-3(CO)(10)(PPh3)(2), were obtained by elimination of the Pt(PBu3t) groups together with one and two CO ligands, respectively. When heated, compound 11 was transformed into the new compound Pt2Os3(CO)(10)(PBu3t)((PBu2CMe2CH2)-C-t)(mu-H) (13) by the loss of two CO ligands and a metalation of one of the methyl groups of one of the PBu3t ligands. Compounds 10-13 have been characterized by single-crystal X-ray diffraction analyses.