At the genesis of our “Pioneers and Influencers” project at Organometallics, the editorial team sought to highlight the careers and contributions of organometallic chemists that perhaps have not received the recognition they deserved. As the project evolved, we decided that the subjects of these editorials should be selected because of the impact they have had on our own career path or scientific interests. For me, one name kept surfacing—Professor Jay Kochi (Figure 1). Figure 1. Photograph of Professor Jay Kochi taken by Beryl Striewski for the University of Houston. This may seem like an odd choice from me. I am not one of Kochi’s former co-workers or colleagues nor am I a contemporary. In fact, I never had the chance to meet him prior to his death in 2008. This choice may also raise a few eyebrows, especially among the more senior members of our field, as Kochi was known to be a cantankerous and intimidating character with many stories of behaviors and incidents well outside of what would be considered acceptable today. So why deem him a Pioneer and Influencer? The answer is his pioneering chemistry.(1) In July 2002, I was six months into my independent career as an Assistant Professor at Cornell University and was attending my first Gordon Research Conference in Organometallic Chemistry.(2) While in Newport, I was thinking of new directions for my research group. One of my first students, Suzanne Bart, was back in Ithaca working on developing catalytic C–C bond-cleavage reactions with rhodium complexes such as Wilkinson’s (Ph₃P)₃RhCl.(3) I became interested in the fundamental question—is there an iron catalyst that can perform chemistry similar to Wilkinson’s compound? Other questions followed—can iron be used instead of palladium in cross coupling? In place of platinum in hydrosilylation? And so on. Over the past 18 years, we have been actively exploring these areas and studying the metal-based radical chemistry of first-row transition metals such as iron, cobalt, and nickel.(4,5) It seems no matter the catalyst we discover or the transformation we are studying, our work somehow relates to the pioneering work of one chemist—Jay Kochi. Long before my independent career and my interests in catalysis with Earth-abundant elements, I was fascinated with a paper of Kochi’s. In the first issue of Organometallics (doi.org/10.1021/om00061a027), he and his co-workers reported a fascinating series of bis(bipyridine)iron dialkyl complexes and studied their C–C bond-forming reductive elimination as a function of oxidation state (Scheme 1). It turns out that many of the lessons learned from this pioneering study have influenced our work on iron-catalyzed [2 + 2] cycloadditions of alkenes to form cyclobutanes.(6) We have since prepared a family of Kochi-inspired iron metallocyclopentane complexes with 1,10-phenanthroline ligands and established the redox activity of the diimine chelates and explored their reactivity toward cyclobutane formation.(7) Metal-catalyzed cross coupling remains one of the success stories of organometallic chemistry and one of the most impactful catalytic reactions in organic chemistry and the pharmaceutical industry.(8) Long before the revolution in palladium catalysis and more recent emphasis on catalysis with Earth-abundant elements, Kochi was exploring variants of the Kharasch reaction and how metal complexes can be used to generate carbon-based radicals. In his own verson of an annus mirabilis, Kochi reported three sequential articles on silver,(9) copper,(10) and iron.(11) Remarkably, low loadings, typically 0.1 mol %, of readily available iron salts such as FeCl₃ promoted the stereospecific alkylation of vinyl halides providing substituted alkenes.(12) Having conducted his Ph.D. studies with George Hammond, Kochi was a mechanistic physical organic chemist at heart.(1b) As such, he and Scott Smith, while at Indiana University, conducted mechanistic studies using product analysis, isotopic labeling studies, and EPR spectroscopy to support formation of iron(I) and iron(III) intermediates.(13) Neidig and co-workers have since reported more detailed spectroscopic studies on the interaction of ferric salts with MeMgBr and identified [MgCl(THF)₅)][FeMe₄] as one of the products observed originally by Kochi.(14) Subsequent studies by the Neidig group identified [MgCl(THF)₅][Fe₈Me₁₂] as the thermally unstable S = 1/2 intermediate reported by Kochi and provided important insight on the complexities of iron speciation during cross coupling.(15) The pioneering work of Kochi nearly 50 years ago paved the way for the contemporary renaissance in iron-catalyzed cross coupling exploring both the mechanistic intricacies of the chemistry(16) and scalable processes for the synthesis of pharmaceuticals.(17,18) The impact of Kochi’s interests in the role of radicals in transition-metal catalysis extends far beyond iron-catalyzed cross coupling. The explosion of what is now termed “metallophotoredox catalysis” and modern nickel-catalyzed cross couplings also trace their origins to the work of Kochi.(19) In addition, Kochi had long-standing interest in metal-catalyzed oxidations and coauthored a seminal and highly cited text with R. A. Sheldon on the topic.(20) The breadth of impactful work leaves no question that Professor Jay Kochi remains a Pioneer and Influencer in organometallic chemistry and mechanistic homogeneous catalysis. Despite his checkered personal legacy, his scientific contributions are nevertheless profound and worthy of highlight. Views expressed in this editorial are those of the author and not necessarily the views of the ACS. This article references 20 other publications. On a more personal note, I think it is important that we openly discuss all aspects of our chemical heritage and history. Understanding those that came before us, their culture, their viewpoints, their views—whether they align with ours or not, serve to shape the present and allow us to move forward as a community. Biographical details for Professor Jay Kochi: https://en.wikipedia.org/wiki/Jay_Kochi.

中文翻译：

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有机金属化学的先驱和影响者：杰伊·高知教授简介

在我们在Organometallics的“先锋和有影响力的人”项目的起源，编辑团队试图强调那些也许没有得到应有认可的有机金属化学家的职业和贡献。随着项目的发展，我们决定选择这些社论的主题，因为它们对我们自己的职业道路或科学兴趣产生了影响。对我而言，一个名字不断出现-Jay Kochi教授（图1）。图1. Beryl Striewski为休斯敦大学拍摄的杰伊·高知教授的照片。对我来说，这似乎是一个奇怪的选择。我不是高知的前同事或同事之一，也不是当代人。实际上，在他2008年去世之前，我从来没有机会见过他。这种选择也可能引起一些人的注意，特别是在我们领域的资深人士中，因为高知被认为是一个贪婪而令人生畏的人物，其行为和事件的许多故事远远超出了当今公认的范围。那为什么认为他先锋和影响者？答案是他的化学开创性。（1）2002年7月，我进入康奈尔大学担任助理教授的职业生涯还只有六个月，还参加了我在有机金属化学领域的第一次戈登研究会议。（2）在纽波特时，我为我的研究小组思考新的方向。我的第一批学生之一苏珊娜·巴特（Suzanne Bart）回到伊萨卡（Ithaca），致力于开发与铑配合物如Wilkinson's（Ph ₃ P）_3的催化C–C键断裂反应RhCl。（3）我对一个基本问题产生了兴趣-是否有一种铁催化剂可以执行与威尔金森化合物相似的化学反应？随之而来的其他问题是：在交叉耦合中可以使用铁代替钯吗？在氢化硅烷化中代替铂？等等。在过去的18年中，我们一直在积极探索这些领域，并研究第一行过渡金属（例如铁，钴和镍）的金属基自由基化学。（4,5）无论我们发现还是发现催化剂，在我们正在研究的转变中，我们的工作与某种化学家杰伊·高知的开创性工作有关。在我从事独立职业和对富含地球的元素进行催化感兴趣之前，我对高知的论文着迷了。在第一期《有机金属》中（doi.org/10.1021/om00061a027），他和他的同事报告了一系列令人着迷的双（联吡啶）二烷基铁二烷基配合物，并研究了它们形成C-C键的还原消除与氧化态的关系（方案1）。事实证明，从这项开创性研究中获得的许多经验影响了我们对铁催化的[2 + 2]烯烃环加成反应生成环丁烷的研究。（6）自此，我们制备了一系列受高知启发的铁金属环戊烷配合物1,10-菲咯啉配体建立了二亚胺螯合物的氧化还原活性，并探索了其对环丁烷形成的反应性。（7）金属催化的交叉偶联仍然是有机金属化学成功的故事之一，也是有机物中最有影响力的催化反应之一。化学和制药工业。（8）早在钯催化的革命和最近对稀土元素催化的强调之前，高知就在探索Kharasch反应的变体，以及如何利用金属络合物生成碳基自由基。在他自己的奇迹年，高知报道银，（9）铜，（10）的三个连续的文章和铁。（11）值得注意的是，低负载量，通常为0.1摩尔％，容易获得的铁盐如的FeCl的₃促进乙烯基的立体有择烷基化卤化物提供取代的烯烃。（12）拥有博士学位。（1b）因此，他和印第安那大学的斯科特·史密斯（Scott Smith）通过产品分析，同位素标记研究和EPR光谱学进行了机理研究，以支持铁的形成。 （I）和铁（III）中间体。（13）此后，Neidig及其同事报道了有关铁盐与MeMgBr相互作用的更详细的光谱研究，并确定了[MgCl（THF）₅）] [FeMe ₄ ]是高知最初观察到的产物之一。（14）Neidig研究小组随后的研究确定[MgCl（THF）₅ ] [Fe ₈ Me ₁₂ ]为热不稳定的S。=高知报道的1/2中间体，并为交叉偶联过程中铁形态的复杂性提供了重要见识。（15）近50年前，高知的开创性工作为当代复兴铁催化交叉偶联研究探索了道路。化学的机械复杂性（16）和药物合成的可扩展过程。（17,18）高知对自由基在过渡金属催化中的作用的兴趣所产生的影响远远超出了铁催化的交叉偶联。现在被称为“金属光氧化还原催化”的爆炸式增长和现代的镍催化的交叉偶联也可以追溯到高知的工作。（19）此外，高知对金属催化的氧化有着长期的兴趣，并共同撰写了一篇开创性的RA Sheldon对此主题进行了高度引用的文字讨论。有机金属化学和机械均相催化的先驱和影响者。尽管他的个人遗产格格不入，但他的科学贡献仍然是深远的，值得一提。本社论中表达的观点只是作者的观点，不一定是ACS的观点。本文引用了其他20种出版物。从个人角度来说，我认为重要的是我们公开讨论化学遗产和历史的各个方面。了解摆在我们面前的那些人，他们的文化，他们的观点，他们的观点（无论它们是否与我们一致），有助于塑造当下并使我们成为一个社区。Jay Kochi教授的履历详情：https：//en.wikipedia.org/wiki/Jay_Kochi。