Addition of Nucleophiles to Phosphanido Derivatives of Pt(III): Formation of P鈥揅, P鈥揘, and P鈥揙 Bonds
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- 作者：Andersson Arias ; Juan Forni茅s ; Consuelo Fortu帽o ; Susana Ib谩帽ez ; Antonio Mart铆n ; Piero Mastrorilli ; Vito Gallo ; Stefano Todisco
- 刊名：Inorganic Chemistry
- 出版年：2013
- 出版时间：October 7, 2013
- 年：2013
- 卷：52
- 期：19
- 页码：11398-11408
- 全文大小：504K
- 年卷期：v.52,no.19(October 7, 2013)
- ISSN：1520-510X
文摘
The reactivity of the dinuclear platinum(III) derivative [(RF)2PtIII(渭-PPh2)2PtIII(RF)2](Pt鈥揚t) (RF = C6F5) (1) toward OH鈥?/sup>, N3鈥?/sup>, and NCO鈥?/sup> was studied. The coordination of these nucleophiles to a metal center evolves with reductive coupling or reductive elimination between a bridging diphenylphosphanido group and OH鈥?/sup>, N3鈥?/sup>, and NCO鈥?/sup> or C6F5 groups and formation of P鈥揙, P鈥揘, or P鈥揅 bonds. The addition of OH鈥?/sup> to 1 evolves with a reductive coupling with the incoming ligand, formation of a P鈥揙 bond, and the synthesis of [NBu4]2[(RF)2PtII(渭-OPPh2)(渭-PPh2)PtII(RF)2] (3). The addition of N3鈥?/sup> takes place through two ways: (a) formation of the P鈥揘 bond and reductive elimination of PPh2N3 yielding [NBu4]2[(RF)2PtII(渭-N3)(渭-PPh2)PtII(RF)2] (4a) and (b) formation of the P鈥揅 bond and reductive coupling with one of the C6F5 groups yielding [NBu4][(RF)2PtII(渭-N3)(渭-PPh2)PtII(RF)(PPh2RF)] (4b). Analogous behavior was shown in the addition of NCO鈥?/sup> to 1 which afforded [NBu4]2[(RF)2PtII(渭-NCO)(渭-PPh2)PtII(RF)2] (5a) and [NBu4][(RF)2PtII(渭-NCO)(渭-PPh2)PtII(RF)(PPh2RF)] (5b). In the reaction of the trinuclear complex [(RF)2PtIII(渭-PPh2)2PtIII(渭-PPh2)2PtII(RF)2](PtIII鈥揚tIII) (2) with OH鈥?/sup> or N3鈥?/sup>, the coordination of the nucleophile takes place selectively at the central platinum(III) center, and the PPh2/OH鈥?/sup> or PPh2/N3鈥?/sup> reductive coupling yields the trinuclear [NBu4]2[(RF)2PtII(渭-Ph2PO)(渭-PPh2)PtII(渭-PPh2)2PtII(RF)2] (6) and [NBu4][(RF)2Pt1(渭3-Ph2PNPPh2)(渭-PPh2)Pt2(渭-PPh2)Pt3(RF)2](Pt2鈥揚t3) (7). Complex 7 is fluxional in solution, and an equilibrium consisting of Pt鈥揚t bond migration was ascertained by 31P EXSY experiments.