Spectroscopic, Magnetic, and Computational Investigations on a Series of Rhenium(III) Cyclopentadienide β-diketiminate Halide and Pseudohalide Complexes,Organometallics

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Spectroscopic, Magnetic, and Computational Investigations on a Series of Rhenium(III) Cyclopentadienide β-diketiminate Halide and Pseudohalide Complexes
Organometallics ( IF 2.5 ) Pub Date : 2021-11-12 , DOI: 10.1021/acs.organomet.1c00516
Erik T. Ouellette _{1,

2} , Jorge Ivan Amaro Estrada ₃ , Daniel J. Lussier ₁ , Khetpakorn Chakarawet ₁ , Trevor D. Lohrey _{1,

2} , Laurent Maron ₃ , Robert G. Bergman ₁ , John Arnold _{1,

2}

Affiliation

The low-valent rhenium(I) salt Na[Re(η⁵-Cp)(BDI)] (BDI = N,N′-bis(2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate) was shown to react with various halide and chalcogenolate reagents, leading to the isolation of a series of rhenium(III)–halide and −pseudohalide complexes: Re(X)(η⁵-Cp)(BDI) (1-X, X = F, Cl, Br, I; 2, X = OTf) and Re(ER)(η⁵-Cp)(BDI) (3-ER, ER = SBn, SeBn, TePh). The ¹H NMR spectra of these complexes displayed sharp resonances shifted several ppm from typical diamagnetic regions, as well as distinct chemical shift trends down both the halide (with the exception of F) and chalcogenolate series, with both Cp and BDI backbone peaks moving downfield with increasing atomic number. Subsequent magnetic susceptibility measurements of the rhenium(III) halides 1-Cl, 1-Br, and 1-I indicated that these complexes display temperature-independent paramagnetism (TIP), with χ_TIP values of 7.41(44) × 10^–4 to 1.50(51) × 10^–3 cm³ mol^–1. Multireference complete active space self-consistent field (CASSCF) computations incorporating spin–orbit state mixing revealed small energy separations (1.7–3.0 kcal/mol) between thermally isolated ground states and the first excited spin–orbit states for the rhenium halides, confirming that low-lying excited states are responsible for the observed TIP behavior.

中文翻译：

一系列铼 (III) 环戊二烯化物 β-二酮亚胺卤化物和拟卤化物配合物的光谱、磁性和计算研究

低价铼 (I) 盐 Na[Re(η ⁵-Cp )(BDI)] (BDI = N , N'-bis (2,6-diisopropylphenyl)-3,5-dimethyl-β-diketiminate)显示可与各种卤化物和硫属元素化物反应，从而分离出一系列铼 (III)-卤化物和-假卤化物配合物：Re(X)(η ⁵ -Cp)(BDI) ( 1-X , X = F , Cl, Br, I; 2 , X = OTf) 和 Re(ER)(η ⁵ -Cp)(BDI) ( 3-ER , ER = SBn, SeBn, TePh)。¹ _这些配合物的 H NMR 光谱显示尖锐的共振从典型的反磁性区域偏移了几个 ppm，以及明显的化学位移趋势向下卤化物（F 除外）和硫族化合物系列，Cp 和 BDI 骨架峰随着增加而向下场移动原子数。随后对铼 (III) 卤化物1-Cl、1-Br和1-I进行的磁化率测量表明，这些配合物显示出与温度无关的顺磁性 (TIP)，χ _TIP值为 7.41(44) × 10 ^–4至1.50(51) × 10 ^–3厘米³摩尔^–1. 结合自旋轨道状态混合的多参考完全活性空间自洽场 (CASSCF) 计算揭示了热隔离基态和卤化铼的第一激发自旋轨道状态之间的小能量分离 (1.7–3.0 kcal/mol)，证实了低位激发态是观察到的 TIP 行为的原因。

更新日期：2021-11-12

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