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Redox chemistry and H-atom abstraction reactivity of a terminal zirconium(IV) oxo compound mediated by an appended cobalt(I) center
Chemical Science ( IF 7.6 ) Pub Date : 2020-09-04 , DOI: 10.1039/d0sc04229c Hongtu Zhang 1, 2, 3, 4 , Gregory P. Hatzis 1, 2, 3, 4 , Diane A. Dickie 4, 5, 6, 7 , Curtis E. Moore 1, 2, 3, 4 , Christine M. Thomas 1, 2, 3, 4
Chemical Science ( IF 7.6 ) Pub Date : 2020-09-04 , DOI: 10.1039/d0sc04229c Hongtu Zhang 1, 2, 3, 4 , Gregory P. Hatzis 1, 2, 3, 4 , Diane A. Dickie 4, 5, 6, 7 , Curtis E. Moore 1, 2, 3, 4 , Christine M. Thomas 1, 2, 3, 4
Affiliation
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The reactivity of the terminal zirconium(IV) oxo complex, O![[triple bond, length as m-dash]](https://www.rsc.org/images/entities/char_e002.gif)
Zr(MesNPiPr2)3CoCNtBu (2), is explored, revealing unique redox activity imparted by the pendent redox active cobalt(I) center. Oxo complex 2 can be chemically reduced using Na/Hg or Ph3C• to afford the ZrIV/Co0 complexes [(μ-Na)OZr(MesNPiPr2)3CoCNtBu]2 (3) and Ph3COZr(MesNPiPr2)3CoCNtBu (4), respectively. Based on the cyclic voltammogram of 2, Ph3˙ should not be sufficiently reducing to achieve the chemical reduction of 2, but sufficient driving force for the reaction is provided by the nucleophilicity of the terminal oxo fragment and its affinity to bind Ph3C+. Accordingly, 2 reacts readily with [Ph3C][BPh4] and Ph3CCl to afford [Ph3COZr(MesNPiPr2)3CoCNtBu][BPh4] ([5][BPh4]) and Ph3COZr(MesNPiPr2)3CoCl (6), respectively. The chemical oxidation of 2 is also investigated, revealing that oxidation of 2 is accompanied by immediate hydrogen atom abstraction to afford the hydroxide complex [HOZr(MesNPiPr2)3CoCNtBu]+ ([9]+). Thus it is posited that the transient [OZr(MesNPiPr2)3CoCNtBu]+ [2]+ cation generated upon oxidation combines the basicity of a nucleophilic early metal oxo fragment with the oxidizing power of the appended cobalt center to facilitate H-atom abstraction.
中文翻译：
末端钴（I）中心介导的末端锆（IV）氧代化合物的氧化还原化学和H原子抽象反应性
探索了末端锆（IV）羰基配合物OZr（MesNP i Pr 2）3 CoCN t Bu（2）的反应活性，揭示了由悬垂的氧化还原活性钴（I）中心赋予的独特氧化还原活性。可以使用Na / Hg或Ph 3 C •还原羰基配合物2，得到Zr IV / Co 0配合物[（μ-Na）OZr（MesNP i Pr 2）3 CoCN t Bu] 2（3）和Ph 3 COZr（MesNPi Pr 2） 3 CoCN t Bu（ 4）。基于的循环伏安图2中，Ph 3 ˙不应被充分减小，以实现化学还原的2，但对于反应足够的驱动力是由终端氧片段的亲核性和其结合博士亲和力提供3 Ç +。因此， 2容易与[Ph 3 C] [BPh 4 ]和Ph 3 CCl反应，得到[Ph 3 COZr（MesNP i Pr 2） 3 CoCNt Bu] [BPh 4 ]（[5] [BPh 4 ]）和Ph 3 COZr（MesNP i Pr 2） 3 CoCl（6）。的化学氧化2还研究，揭示的氧化2是伴随着即时氢原子夺取，得到氢氧化物复合物[HOZr（MesNP我镨2） 3 CoCN吨卜] +（[9] +）。因此，假定瞬态[OZr（MesNP i Pr 2） 3氧化时生成的CoCN t Bu] + [ 2 ] +阳离子将亲核性的早期金属氧代片段的碱性与附加的钴中心的氧化能力结合在一起，以促进H原子的提取。
更新日期：2020-10-14
Zr(MesNPiPr2)3CoCNtBu (2), is explored, revealing unique redox activity imparted by the pendent redox active cobalt(I) center. Oxo complex 2 can be chemically reduced using Na/Hg or Ph3C• to afford the ZrIV/Co0 complexes [(μ-Na)OZr(MesNPiPr2)3CoCNtBu]2 (3) and Ph3COZr(MesNPiPr2)3CoCNtBu (4), respectively. Based on the cyclic voltammogram of 2, Ph3˙ should not be sufficiently reducing to achieve the chemical reduction of 2, but sufficient driving force for the reaction is provided by the nucleophilicity of the terminal oxo fragment and its affinity to bind Ph3C+. Accordingly, 2 reacts readily with [Ph3C][BPh4] and Ph3CCl to afford [Ph3COZr(MesNPiPr2)3CoCNtBu][BPh4] ([5][BPh4]) and Ph3COZr(MesNPiPr2)3CoCl (6), respectively. The chemical oxidation of 2 is also investigated, revealing that oxidation of 2 is accompanied by immediate hydrogen atom abstraction to afford the hydroxide complex [HOZr(MesNPiPr2)3CoCNtBu]+ ([9]+). Thus it is posited that the transient [OZr(MesNPiPr2)3CoCNtBu]+ [2]+ cation generated upon oxidation combines the basicity of a nucleophilic early metal oxo fragment with the oxidizing power of the appended cobalt center to facilitate H-atom abstraction.
中文翻译：
末端钴（I）中心介导的末端锆（IV）氧代化合物的氧化还原化学和H原子抽象反应性
探索了末端锆（IV）羰基配合物O
Zr（MesNP i Pr 2）3 CoCN t Bu（2）的反应活性，揭示了由悬垂的氧化还原活性钴（I）中心赋予的独特氧化还原活性。可以使用Na / Hg或Ph 3 C •还原羰基配合物2，得到Zr IV / Co 0配合物[（μ-Na）OZr（MesNP i Pr 2）3 CoCN t Bu] 2（3）和Ph 3 COZr（MesNPi Pr 2） 3 CoCN t Bu（ 4）。基于的循环伏安图2中，Ph 3 ˙不应被充分减小，以实现化学还原的2，但对于反应足够的驱动力是由终端氧片段的亲核性和其结合博士亲和力提供3 Ç +。因此， 2容易与[Ph 3 C] [BPh 4 ]和Ph 3 CCl反应，得到[Ph 3 COZr（MesNP i Pr 2） 3 CoCNt Bu] [BPh 4 ]（[5] [BPh 4 ]）和Ph 3 COZr（MesNP i Pr 2） 3 CoCl（6）。的化学氧化2还研究，揭示的氧化2是伴随着即时氢原子夺取，得到氢氧化物复合物[HOZr（MesNP我镨2） 3 CoCN吨卜] +（[9] +）。因此，假定瞬态[OZr（MesNP i Pr 2） 3氧化时生成的CoCN t Bu] + [ 2 ] +阳离子将亲核性的早期金属氧代片段的碱性与附加的钴中心的氧化能力结合在一起，以促进H原子的提取。
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