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用电喷雾电离串联质谱法通过动力学方法研究铂(II)乙二胺配合物中竞争性吡啶损失。

Electrospray ionization tandem mass spectrometric studies of competitive pyridine loss from platinum(II) ethylenediamine complexes by the kinetic method.

作者信息

Holmes R J, O'Hair R A, McFadyen W D

机构信息

School of Chemistry, University of Melbourne, Victoria 3010, Australia.

出版信息

Rapid Commun Mass Spectrom. 2000;14(24):2385-92. doi: 10.1002/1097-0231(20001230)14:24<2385::AID-RCM172>3.0.CO;2-M.

DOI:10.1002/1097-0231(20001230)14:24<2385::AID-RCM172>3.0.CO;2-M
PMID:11114055
Abstract

The competition between pyridine ligand loss in square planar Pt(II) complexes has been examined using the doubly and singly charged ions of complexes consisting of platinum(ethylenediamine) coordinated to two different substituted pyridines. Collision induced dissociation (CID) of Pt(en)Py(1)Py(2) (where Py(1) = one of ten different substituted pyridines and Py(2) = pyridine) results in loss of the protonated pyridines to yield the singly charged platinum ions Pt(en)Py(1)-H and Pt(en)Py(2)-H. In contrast, fragmentation of Pt(en)Py(1)Py(2)-H results in neutral pyridine loss to yield the ions Pt(en)Py(1)-H and Pt(en)Py(2)-H. In the latter case, the correlation between relative losses of each pyridine compared to their gas-phase proton affinities is poor. A novel chloride ion abstraction reaction occurs for the fragmentation of Pt(en)Py(1)Py(2) when Py(1) = o-C(5)H(4)CIN and Py(2) = C(5)H(5)N, to yield the Pt(en)(Cl)Py(2) and o-C(5)H(4)N pair of ions. In order to model this process the competition between nitrogen and chlorine binding in Pt(NH(3))(3)(o-NC(5)H(4)Cl) has been examined using density functional theory (DFT) calculations at the B3LYP/LANL2DZ level of theory. Both adducts are minima with the N adduct being more stable than the Cl adduct by 22.7 kcal mol(-1). Furthermore, the Cl adduct exhibits a significant stretching of the C-Cl bond (to 1.935 A), consistent with the observed chloride ion abstraction reaction, which is endothermic by 9.0 kcal mol(-1) (relative to the N adduct).

摘要

利用由铂(乙二胺)与两种不同取代吡啶配位形成的配合物的双电荷和单电荷离子,研究了平面正方形铂(II)配合物中吡啶配体损失的竞争情况。[Pt(en)Py(1)Py(2)]²⁺(其中Py(1)为十种不同取代吡啶之一,Py(2)为吡啶)的碰撞诱导解离(CID)导致质子化吡啶损失,生成单电荷铂离子[Pt(en)Py(1)-H]⁺和[Pt(en)Py(2)-H]⁺。相比之下,[Pt(en)Py(1)Py(2)-H]⁺的碎片化导致中性吡啶损失,生成离子[Pt(en)Py(1)-H]⁺和[Pt(en)Py(2)-H]⁺。在后一种情况下,每种吡啶的相对损失与其气相质子亲和力之间的相关性较差。当Py(1)=邻-C₅H₄CIN且Py(2)=C₅H₅N时,[Pt(en)Py(1)Py(2)]²⁺的碎片化发生了一种新颖的氯离子夺取反应,生成[Pt(en)(Cl)Py(2)]⁺和[邻-C₅H₄N]⁺这对离子。为了模拟这一过程,使用密度泛函理论(DFT)在B3LYP/LANL2DZ理论水平上研究了[Pt(NH₃)₃(邻-NC₅H₄Cl)]²⁺中氮和氯配位的竞争情况。两种加合物都是极小值,N加合物比Cl加合物更稳定,稳定22.7 kcal·mol⁻¹。此外,Cl加合物表现出C-Cl键明显伸长(至1.935 Å),这与观察到的氯离子夺取反应一致,该反应吸热9.0 kcal·mol⁻¹(相对于N加合物)。

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