Bratsos Ioannis, Calmo Simone, Zangrando Ennio, Balducci Gabriele, Alessio Enzo
Department of Chemical and Pharmaceutical Sciences, Università di Trieste , Via L. Giorgieri 1, 34127 Trieste, Italy.
Inorg Chem. 2013 Oct 21;52(20):12120-30. doi: 10.1021/ic401940z. Epub 2013 Oct 3.
The preparation and structural characterization of three cationic Ru(II)-dmso carbonyls and of four neutral mono- and dicarbonyl Os(II)-dmso derivatives is reported. The two monocarbonyl species fac-[Ru(CO)(dmso-O)3(dmso-S)2][PF6]2 (11) and cis,cis,cis-[RuCl(CO)(dmso-O)2(dmso-S)2][PF6] (12) were obtained from the neutral monocarbonyl precursor cis,trans,cis-[RuCl2(CO)(dmso-O)(dmso-S)2] (3) upon stepwise replacement of the chlorides with dmso, that binds in each case through the oxygen atom. The dicarbonyl cationic complex cis,cis,trans-[Ru(CO)2(dmso-O)2(dmso-S)Cl][PF6] (13) was instead obtained upon treatment of the neutral tricarbonyl precursor fac-[RuCl2(CO)3(dmso-O)] (8) with AgPF6 in the presence of DMSO: replacement of a Cl(-) with a dmso-O implied also the substitution of one CO ligand by another dmso (that binds through S trans to Cl). The Os(II) carbonyls trans,trans,trans-[OsCl2(CO)(dmso-O)(dmso-S)2] (17), trans,cis,cis-[OsCl2(CO)2(dmso-O)2] (18), cis,mer-[OsCl2(CO)(dmso-S)3] (19), and cis,trans,cis-[OsCl2(CO)(dmso-O)(dmso-S)2] (20) were obtained by treatment of the Os(II)-dmso precursors trans-[OsCl2(dmso-S)4] (14) and cis,fac-[OsCl2(dmso-O)(dmso-S)3] (15) with CO. Each one of them is structurally similar to an already known Ru(II) analog, even though--in agreement with the expected greater inertness of Os(II)--more forcing reaction conditions were required for their preparation. Interestingly, compound 20 could not be isolated in pure form, but only as a 1:1 cocrystallized mixture with its precursor 15. The dmso ligand is always bound through the oxygen atom when trans to CO. We are confident that the new Ru(II)- and Os(II)-dmso carbonyl species described here represent a contribution to expand the pool of complexes bearing some easily replaceable dmso ligands to be used as well-behaved precursors in inorganic synthesis.
本文报道了三种阳离子钌（II）-二甲基亚砜羰基化合物以及四种中性单羰基和二羰基锇（II）-二甲基亚砜衍生物的制备及其结构表征。两种单羰基化合物顺，顺，顺-[RuCl(CO)(dmso - O)₂(dmso - S)₂][PF₆]（11）和 fac-[Ru(CO)(dmso - O)₃(dmso - S)₂][PF₆]₂（12）是由中性单羰基前体顺，反，顺-[RuCl₂(CO)(dmso - O)(dmso - S)₂]（3）通过用二甲基亚砜逐步取代氯化物得到的，二甲基亚砜在每种情况下均通过氧原子配位。相反，二羰基阳离子配合物顺，顺，反-[Ru(CO)₂(dmso - O)₂(dmso - S)Cl][PF₆]（13）是在二甲基亚砜存在下，用 AgPF₆处理中性三羰基前体 fac-[RuCl₂(CO)₃(dmso - O)]（8）得到的：用二甲基亚砜 - O取代一个 Cl⁻也意味着一个 CO 配体被另一个二甲基亚砜（通过 S 与 Cl 反位配位）取代。锇（II）羰基化合物反，反，反-[OsCl₂(CO)(dmso - O)(dmso - S)₂]（17）、反，顺，顺-[OsCl₂(CO)₂(dmso - O)₂]（18）、顺，反-[OsCl₂(CO)(dmso - S)₃]（19）和顺，反，顺-[OsCl₂(CO)(dmso - O)(dmso - S)₂]（20）是通过用 CO 处理锇（II）-二甲基亚砜前体反-[OsCl₂(dmso - S)₄]（14）和顺，面-[OsCl₂(dmso - O)(dmso - S)₃]（15）得到的。它们中的每一个在结构上都与一种已知的钌（II）类似物相似，尽管——与预期的锇（II）更大惰性一致——它们的制备需要更苛刻的反应条件。有趣的是，化合物 20 不能以纯形式分离出来，而只能作为与其前体 15 的 1:1 共结晶混合物得到。当二甲基亚砜配体与 CO 反位时，它总是通过氧原子配位。我们相信，本文描述的新型钌（II）和锇（II）-二甲基亚砜羰基化合物有助于扩大带有一些易于取代的二甲基亚砜配体的配合物库，这些配合物可作为无机合成中性能良好的前体。
