A series of new models for the active site of [NiFe]-H₂ases have been prepared by simple and convenient methods. Thus, treatment of diphosphine-chelated Ni dichlorides [R(CH₂PPh₂)₂]NiCl₂ (R = MeN, CH₂, nil) with (dppv)(CO)₂Fe(pdt) (dppv = 1,2-C₂H₂(PPh₂)₂, pdt = 1,3-propanedithiolate) and NaBF₄ gave dicarbonyl models {[R(CH₂PPh₂)₂]Ni(pdt)Fe(CO)₂(dppv)}(BF₄)₂ (R = MeN, [1a](BF₄)₂; R = CH₂, [1b](BF₄)₂; R = nil, [1c](BF₄)₂) and μ-chloro models {[R(CH₂PPh₂)₂]Ni(pdt)(μ-Cl)Fe(CO)(dppv)}(BF₄) (R = MeN, [2a](BF₄); R = CH₂, [2b](BF₄); R = nil, [2c](BF₄)). Further treatment of [1a](BF₄)₂–[1c](BF₄)₂ with Me₃NO·2H₂O afforded μ-hydroxo models {[R(CH₂PPh₂)₂]Ni(pdt)(μ-OH)Fe(CO)(dppv)}(BF₄) (R = MeN, [3a](BF₄); R = CH₂, [3b](BF₄); R = nil, [3c](BF₄)), whereas t-fluorido models {[R(CH₂PPh₂)₂]Ni(pdt)Fe(CO)(t-F)(dppv)}(BF₄) (R = MeN, [4a](BF₄); R = CH₂, [4b](BF₄); R = nil, [4c](BF₄)) could be prepared by further treatment of [3a](BF₄)–[3c](BF₄) with HBF₄·Et₂O. While the first t-bicarbonato models {[R(CH₂PPh₂)₂]Ni(pdt)Fe(CO)(t-OCO₂H)(dppv)}(BF₄) (R = MeN, [5a](BF₄); R = CH₂, [5b](BF₄); R = nil, [5c](BF₄)) were prepared by CO₂ fixation reactions of [3a](BF₄)–[3c](BF₄) with 0.8 MPa CO₂, the esterification reactions of [5a](BF₄)–[5c](BF₄) with MeOH or the CO₂ fixation reactions of [1a](BF₄)₂–[1c](BF₄)₂ with Me₃NO and in situ generated CO₂ in MeOH yielded the first t-carbonato models {[R(CH₂PPh₂)₂]Ni(pdt)Fe(CO)(t-OCO₂Me)(dppv)}(BF₄) (R = MeN, [6a](BF₄); R = CH₂, [6b](BF₄); R = nil, [6c](BF₄)). All possible pathways for production of these new model complexes are briefly discussed, and their molecular structures were fully characterized by various spectroscopies and confirmed for some of them by X-ray crystallography.

中文翻译：

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[NiFe] -Hydrogenases的活性位点相关的功能化的镍-二硫代镍铁的合成，表征和反应

通过简单方便的方法，制备了一系列[NiFe] -H ₂活性炭的新模型。因此，处理二膦螯合的Ni酰氯的[R（CH ₂ PPH ₂）₂ ]的NiCl ₂（R = MEN，CH ₂，无）与（dppv）（CO）₂的Fe（PDT）（dppv = 1,2- C ₂ H ₂（PPh ₂）₂，pdt = 1,3-丙二硫醇盐）和NaBF ₄给出二羰基模型{[R（CH ₂ PPh ₂）₂ ] Ni（pdt）Fe（CO）₂（dppv）}（BF ₄）₂（R = MeN，[1a ]（BF ₄）₂；R = CH ₂，[ 1b ]（BF ₄）₂；R = nil，[ 1c ]（BF ₄）₂）和μ-氯模型{[R（CH ₂ PPh ₂）₂ ] Ni（pdt）（μ-Cl）Fe（CO）（dppv）}（BF ₄） （R ＝ MeN，[ 2a ]（BF ₄）； R ＝ CH ₂，[ 2b ]（BF ₄； R ＝ nil，[ 2c ]（BF ₄））。[ 1a ]（BF ₄）_2- [ 1c的进一步处理具有Me ₃ NO·2H ₂ O的]（BF ₄）₂提供了μ-羟基模型{[R（CH ₂ PPh ₂）₂ ] Ni（pdt）（μ-OH）Fe（CO）（dppv）}（BF ₄）（R = MeN，[ 3a ]（BF ₄）; R = CH ₂，[ 3b ]（BF ₄）; R = nil，[ 3c ]（BF ₄）），而t-氟代模型{[R（CH ₂ PPh ₂）₂ ] Ni（pdt）Fe（CO）（t -F）（dppv）}（BF ₄）（R = MeN，[ 4a ]（BF ₄）; R ＝ CH ₂，[ 4b ]（BF ₄）；m ＝₁。R =零，[ 4C ]（BF ₄））可以通过[进一步处理来制备3A ]（BF ₄） - [ 3C ]（BF ₄）与HBF ₄ ·的Et ₂ O.虽然第一吨-bicarbonato模型{ [R（CH ₂ PPh ₂）₂ ] Ni（pdt）Fe（CO）（t -OCO ₂ H）（dppv）}（BF ₄）（R = MeN，[ 5a ]（BF ₄）; R = CH ₂，[ 5b ]（BF ₄）; R =无，通过[ 3a ]（BF ₄）– [ 3c ]（BF ₄）与0.8 MPa CO ₂的CO ₂固定反应，[ 5a ]（BF）的酯化反应制备[ 5c ]（BF ₄））₄）– [ 5c ]（BF ₄）与MeOH或[ 1a ]（BF ₄）₂ – [ 1c ]（BF ₄）₂与Me ₃ NO的CO ₂固定反应，并在MeOH中原位生成CO ₂，得到第一Ť-carbonato模型{[R（CH ₂ PPh ₂）₂ ] Ni（pdt）Fe（CO）（t -OCO ₂ Me）（dppv）}（BF ₄）（R = MeN，[ 6a ]（BF ₄）; R ＝ CH ₂，[ 6b ]（BF ₄）； R ＝ nil，[ 6c ]（BF ₄））。简要讨论了产生这些新模型复合物的所有可能途径，并通过各种光谱学对它们的分子结构进行了充分表征，并通过X射线晶体学对其进行了确认。