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Formation of Heterobimetallic Complexes by Addition of d10-Metal Ions to cis-[(dppe)M(κC-2-C6F4PPh2)2] (M = Ni, Pd, and Pt)
Organometallics ( IF 2.8 ) Pub Date : 2017-08-28 00:00:00 , DOI: 10.1021/acs.organomet.7b00145
Robert Gericke 1, 2 , Martin A. Bennett 3 , Steven H. Privér 1 , Suresh K. Bhargava 1
Affiliation  

The reactivity of [(dppe)M(κC-2-C6F4PPh2)2] (M = Ni (1Ni), Pd (1Pd), and Pt (1Pt); dppe = 1,2-bis(diphenylphosphino)ethane)) toward monovalent coinage metal ions (M′ = Cu, Ag, and Au) has been investigated. Two main isomers [(dppe)M(κC-2-C6F4PPh2)(μ-2-C6F4PPh2)M′Cl] (2PdAg, 2PdAu, 2PtCu, 2PtAg, and 2PtAu) and [(dppe)M(μ-2-C6F4PPh2)2M′Cl] (3PdCu, 3PdAg, and 3PtCu) could be detected. Quantum chemical calculations underpin the enhanced thermodynamic stability of [(dppe)M(κC-2-C6F4PPh2)(μ-2-C6F4PPh2)M′Cl] for combinations of the heavier metals. NBO calculations reveal attractive Pt···Cu and Pt···Ag interactions in complexes 2PtCu and 2PtAg, respectively. From the reaction of [(dppe)M(κC-2-C6F4PPh2)2] with an excess of [AuCl(tht)], a series of trinuclear complexes [(dppe)M(μ-2-C6F4PPh2)2(AuCl)2] (4NiAu2, 4PdAu2, and 4PtAu2) was prepared. Reaction of [(dppe)M(κC-2-C6F4PPh2)(μ-2-C6F4PPh2)M′Cl] with TlPF6 leads to the formation of cationic derivatives [(dppe)M(μ-2-C6F4PPh2)2M′]PF6 with P–M′–P (6PtAu) or P–M′–C (7PdAu, 7PtAu) bonding situations around the coinage metal.

中文翻译:

双核配合物的形成通过d的添加10 -金属离子,以顺式- [(DPPE)M(κ ç -2-C 6 ˚F 4 PPH 22 ](M =镍,钯,和Pt)

[(dppe)M(κC-2- C6 F 4 PPh 22 ]的反应性(M = Ni(1Ni),Pd(1Pd)和Pt(1Pt); dppe = 1,2-双(二苯基膦基) )乙烷))向单价造价金属离子(M'= Cu,Ag和Au)进行了研究。两个主要的异构体[(DPPE)M(κ ç -2-C 6 ˚F 4 PPH 2)(μ-2-C 6 ˚F 4 PPH 2)M'Cl](2PdAg2PdAu2PtCu2PtAg,和2PtAu)和[(dppe)M(μ-2- C6 F可以检测到4 PPh 22 M'Cl](3PdCu3PdAg3PtCu)。量子化学计算托换的增强的热力学稳定性[(DPPE)M(κ ç -2-C 6 ˚F 4 PPH 2)(μ-2-C 6 ˚F 4 PPH 2)M'Cl用于较重的金属的组合。NBO计算揭示了复合物2PtCu2PtAg中有吸引力的Pt···Cu和Pt···Ag相互作用。从[(dppe)M(κC-2- C6 F 4 PPh 22的反应]用过量的[AUCL(THT)],一系列三核配合物[(DPPE)M(μ-2-C 6 ˚F 4 PPH 22(AUCL)2 ](4NiAu 24PdAu 2,和4PtAu 2)已准备好。的反应[(DPPE)M(κ ç -2-C 6 ˚F 4 PPH 2)(μ-2-C 6 ˚F 4 PPH 2)M'Cl]与TlPF 6个通向阳离子衍生物的形成[(DPPE) M(μ-2- C6 F 4 PPh 22 M'] PF图6所示的硬币金属周围有P–M'–P(6PtAu)或P–M'–C(7PdAu7PtAu)键合情况。
更新日期:2017-08-29
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