Abstract
A decanuclear silver chalcogenide cluster, [Ag10(Se){Se2P(OiPr)2}8] (2) was isolated from a hydride-encapsulated silver diisopropyl diselenophosphates, [Ag7(H){Se2P(OiPr)2}6], under thermal condition. The time-dependent NMR spectroscopy showed that 2 was generated at the first three hours and the hydrido silver cluster was completely consumed after thirty-six hours. This method illustrated as cluster-to-cluster transformations can be applied to prepare selenide-centered decanuclear bimetallic clusters, [CuxAg10-x(Se){Se2P(OiPr)2}8] (x = 0–7, 3), via heating [CuxAg7−x(H){Se2P(OiPr)2}6] (x = 1–6) at 60 °C. Compositions of 3 were accurately confirmed by the ESI mass spectrometry. While the crystal 2 revealed two un-identical [Ag10(Se){Se2P(OiPr)2}8] structures in the asymmetric unit, a co-crystal of [Cu3Ag7(Se){Se2P(OiPr)2}8]0.6[Cu4Ag6(Se){Se2P(OiPr)2}8]0.4 ([3a]0.6[3b]0.4) was eventually characterized by single-crystal X-ray diffraction. Even though compositions of 2, [3a]0.6[3b]0.4 and the previous published [Ag10(Se){Se2P(OEt)2}8] (1) are quite similar (10 metals, 1 Se2−, 8 ligands), their metal core arrangements are completely different. These results show that different synthetic methods by using different starting reagents can affect the structure of the resulting products, leading to polymorphism.
Highlights
In pursuit of metal chalcogenide clusters, Group 11 elements (Cu, Ag, Au) are frequently employed in the synthesis of novel clusters [1,2,3,4]
Silver chalcogenide clusters have rich structural varieties which can be synthesized by many different approaches [5,6,7,8,9,10,11]
In the construction of high-nuclearity silver chalcogenide clusters stabilized by phosphine, chalcogenolate, halide, carboxylate, or alkynyl ligands [6,7,8,9,10,11]
Summary
In pursuit of metal chalcogenide clusters, Group 11 elements (Cu, Ag, Au) are frequently employed in the synthesis of novel clusters [1,2,3,4]. Different diphosphine lig ands (bis(diphenylphosphinol)propane, dppp) used in the previous reaction at −30 ◦ C produce [Ag172 Se40 (Sen Bu) (dppp)4 ], which increases the cluster nuclearity and keeps similar cross sections of Ag2 Se as that found in Ag114 Se34 [6]. Another mega cluster synthesized by the reaction of CF3 CO2 Ag, dppm, PhS(SiMe3 ) and S(SiMe3 ) at −40 ◦ C yielded [Ag70 S20 (PhS) (dppm)10 ](CF3 CO2 )2 [7]. Compared with those giant silver chalcogenide clusters which are the kinetic products formed in different reaction temperatures, smaller silver chalcogenide clusters encapsulated with a single
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