<br>A 型框架模板高配位铂 (IV) 顺式双硼基配合物,Inorganic Chemistry

当前位置： X-MOL 学术 › Inorg. Chem. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

A 型框架模板高配位铂 (IV) 顺式双硼基配合物
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2024-05-25 , DOI: 10.1021/acs.inorgchem.4c01141
Max Passargus _{1,

2} , Merle Arrowsmith _{1,

2} , Rüdiger Bertermann _{1,

2} , Maik Finze _{1,

2} , Holger Braunschweig _{1,

2}

Affiliation

Et ₂ O·BF ₃或Me ₂ S·BCl ₃添加到BNBN-积聚烯桥接的Pt(II) A-框架配合物[(μ-1,1-BNBN(TMS) ₂ )(μ-dmpm) ₂ Pt ₂ X ₂ ] (TMS = SiMe ₃ , dmpm = CH ₂ (PMe ₂ ) ₂ , X = Br 1 ^Br , I 1 ^I ) 分别导致一个 B–F 或 B–Cl 键的氧化加成，到桥接亚氨基硼烷类 B–NeqB–N 部分的内部 BN 键，并且一个 Pt(II) 中心与所得的相邻 BF ₂ （复合物2 ^Br -F ）或 BCl ₂ （复合物2 ^Br分别是-Cl和^2I -Cl )部分。 X射线晶体学和多核核磁共振波谱数据表明， 2 ^Br -F中的Pt→BF ₂相互作用非常弱且仅为静电作用，而2 ^Br -Cl和2 ^I -Cl中的Pt→BCl ₂相互作用更强。供体-受体债券。相反，Me ₂ S·BBr ₃与1 ^Br的反应产生约。类似的 B-Br 加成产物与亚氨基硼烷2 ^Br -Br的 3:2 混合物，以及随后螯合 BBr ₂部分的一个 B-Br 键与相邻铂中心氧化加成的产物，即混合-价硼烷二基桥连，Pt(II)–Pt(IV)-溴硼基络合物3-Br ₅ 。 Me ₂ S·BI ₃与1 ^Br和 Me ₂ S·BBr ₃与1 ^I的类似反应产生了 Pt(II)–Pt(II)-硼烷的复杂产物混合物（ 2 ^Br -I和2 ^I -Br ，分别）和 Pt(II)–Pt(IV)-硼基络合物 ( 3-Br _n I _{5– n} , n = 1–3) 分别类似于2 ^X -Y和3-Br ₅ ，后者的比例随着前体混合物中碘化物的比例而增加。多核核磁共振波谱和 X 射线晶体学数据都表明，软的、与碘化物亲和的铂中心和更硬的、与溴化物亲和的硼中心之间存在复杂且广泛的分子间和分子内溴化物-碘化物交换。 BBr ₂ Ar (Ar = 2,4,6-Me ₃ C ₆ H ₂ (Mes), 2,3,5,6-Me ₄ C ₆ H 的反应提供了这些卤化物交换机制的线索(Dur)) 与1 ^Br ，产生2 ^Br -Br的阳离子 Pt(II)–Pt(II)-硼类似物，复合物4 ^Br -Ar ，由空间诱导的溴化物取代基从螯合 Pt→BBrAr 部分，并显示稀有金属→硼供体-受体键。

"点击查看英文标题和摘要"

A-Frame-Templated High-Coordinate Platinum(IV) cis-Bis(boryl) Complexes

The addition of Et₂O·BF₃ or Me₂S·BCl₃ to the BNBN-cumulene-bridged Pt(II) A-frame complexes [(μ-1,1-BNBN(TMS)₂)(μ-dmpm)₂Pt₂X₂] (TMS = SiMe₃, dmpm = CH₂(PMe₂)₂, X = Br 1^Br, I 1^I) resulted in the oxidative addition of one B–F or B–Cl bond, respectively, to the internal BN bond of the bridging, iminoborane-like B–N≡B–N moiety, and coordination of one Pt(II) center to the resulting adjacent BF₂ (complex 2^Br-F) or BCl₂ (complexes 2^Br-Cl and 2^I-Cl) moiety, respectively. X-ray crystallographic and multinuclear NMR-spectroscopic data show that the Pt→BF₂ interaction in 2^Br-F is very weak and merely electrostatic, while the Pt→BCl₂ interaction in 2^Br-Cl and 2^I-Cl is a stronger donor–acceptor bond. In contrast, the reaction of Me₂S·BBr₃ with 1^Br yielded a ca. 3:2 mixture of the analogous B–Br addition product to the iminoborane, 2^Br-Br, and the product of a subsequent oxidative addition of one B–Br bond of the chelating BBr₂ moiety to the adjacent platinum center, the mixed-valence boranediyl-bridged, Pt(II)–Pt(IV)-bromoboryl complex 3-Br₅. The analogous reactions of Me₂S·BI₃ with 1^Br and Me₂S·BBr₃ with 1^I yielded complex product mixtures of Pt(II)–Pt(II)-borane (2^Br-I and 2^I-Br, respectively) and Pt(II)–Pt(IV)-boryl complexes (3-Br_nI_5–n, n = 1–3) analogous to 2^X-Y and 3-Br₅, respectively, the proportion of the latter increasing with the proportion of iodide in the precursor mixture. Both multinuclear NMR-spectroscopic and X-ray crystallographic data show evidence of complex and extensive inter- and intramolecular bromide–iodide exchanges between the soft, iodide-affine platinum centers and the harder, more bromide-affine boron centers. A clue to the mechanism of these halide exchanges is provided by the reactions of BBr₂Ar (Ar = 2,4,6-Me₃C₆H₂ (Mes), 2,3,5,6-Me₄C₆H (Dur)) with 1^Br, which yielded the cationic Pt(II)–Pt(II)-borenium analogues of 2^Br-Br, the complexes 4^Br-Ar, generated by the sterics-induced displacement of the bromide substituent from the chelating Pt→BBrAr moiety, and displaying a rare metal→borenium donor–acceptor bond.

更新日期：2024-05-25

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南