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Homogeneous Functionalization of Methane
Chemical Reviews ( IF 51.4 ) Pub Date : 2017-05-01 00:00:00 , DOI: 10.1021/acs.chemrev.6b00739 Niles Jensen Gunsalus 1 , Anjaneyulu Koppaka 1 , Sae Hume Park 1 , Steven M. Bischof 1 , Brian G. Hashiguchi 1 , Roy A. Periana 1
Chemical Reviews ( IF 51.4 ) Pub Date : 2017-05-01 00:00:00 , DOI: 10.1021/acs.chemrev.6b00739 Niles Jensen Gunsalus 1 , Anjaneyulu Koppaka 1 , Sae Hume Park 1 , Steven M. Bischof 1 , Brian G. Hashiguchi 1 , Roy A. Periana 1
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One of the remaining “grand challenges” in chemistry is the development of a next generation, less expensive, cleaner process that can allow the vast reserves of methane from natural gas to augment or replace oil as the source of fuels and chemicals. Homogeneous (gas/liquid) systems that convert methane to functionalized products with emphasis on reports after 1995 are reviewed. Gas/solid, bioinorganic, biological, and reaction systems that do not specifically involve methane functionalization are excluded. The various reports are grouped under the main element involved in the direct reactions with methane. Central to the review is classification of the various reports into 12 categories based on both practical considerations and the mechanisms of the elementary reactions with methane. Practical considerations are based on whether or not the system reported can directly or indirectly utilize O2 as the only net coreactant based only on thermodynamic potentials. Mechanistic classifications are based on whether the elementary reactions with methane proceed by chain or nonchain reactions and with stoichiometric reagents or catalytic species. The nonchain reactions are further classified as CH activation (CHA) or CH oxidation (CHO). The bases for these various classifications are defined. In particular, CHA reactions are defined as elementary reactions with methane that result in a discrete methyl intermediate where the formal oxidation state (FOS) on the carbon remains unchanged at −IV relative to that in methane. In contrast, CHO reactions are defined as elementary reactions with methane where the carbon atom of the product is oxidized and has a FOS less negative than −IV. This review reveals that the bulk of the work in the field is relatively evenly distributed across most of the various areas classified. However, a few areas are only marginally examined, or not examined at all. This review also shows that, while significant scientific progress has been made, greater advances, particularly in developing systems that can utilize O2, will be required to develop a practical process that can replace the current energy and capital intensive natural gas conversion process. We believe that this classification scheme will provide the reader with a rapid way to identify systems of interest while providing a deeper appreciation and understanding, both practical and fundamental, of the extensive literature on methane functionalization. The hope is that this could accelerate progress toward meeting this “grand challenge.”
中文翻译：
甲烷的均相官能化
化学方面尚待解决的“巨大挑战”之一就是开发下一代，更便宜，更清洁的工艺，该工艺可以利用天然气中大量的甲烷来增加或替代石油作为燃料和化学物质的来源。审查了将甲烷转化为功能化产品的均质（气/液）系统，重点是1995年以后的报告。不包括不涉及甲烷功能化的气体/固体，生物无机，生物和反应系统。各种报告归类为与甲烷直接反应所涉及的主要因素。审查的中心是根据实际考虑和与甲烷发生基本反应的机制，将各种报告分为12类。2个作为仅基于热力学势的唯一净共反应剂。机械分类基于与甲烷的基本反应是通过链反应还是非链反应以及化学计量的试剂或催化物质进行。非链反应进一步分类为CH活化（CHA）或CH氧化（CHO）。定义了这些各种分类的基础。特别地，CHA反应被定义为与甲烷发生的元素反应，该反应会生成离散的甲基中间体，其中碳上的形式氧化态（FOS）相对于甲烷而言处于-IV。相反，CHO反应被定义为与甲烷的基本反应，其中产物的碳原子被氧化，且FOS的负值小于-IV。这项审查表明，该领域的大部分工作相对平均地分布在所有分类的领域中。但是，仅对某些区域进行了边际检查，或者根本没有进行检查。这项审查还表明，尽管科学取得了重大进展，但取得了更大的进步，特别是在开发可以利用O的系统中参照图2，将需要开发可替代当前能源和资本密集型天然气转化过程的实用过程。我们相信，这种分类方案将为读者提供一种快速识别感兴趣的系统的方法，同时对甲烷功能化的广泛文献提供更深入的理解和理解，包括实际和基础知识。希望这可以加快实现这一“巨大挑战”的速度。
更新日期：2017-05-01
中文翻译：
甲烷的均相官能化
化学方面尚待解决的“巨大挑战”之一就是开发下一代，更便宜，更清洁的工艺，该工艺可以利用天然气中大量的甲烷来增加或替代石油作为燃料和化学物质的来源。审查了将甲烷转化为功能化产品的均质（气/液）系统，重点是1995年以后的报告。不包括不涉及甲烷功能化的气体/固体，生物无机，生物和反应系统。各种报告归类为与甲烷直接反应所涉及的主要因素。审查的中心是根据实际考虑和与甲烷发生基本反应的机制，将各种报告分为12类。2个作为仅基于热力学势的唯一净共反应剂。机械分类基于与甲烷的基本反应是通过链反应还是非链反应以及化学计量的试剂或催化物质进行。非链反应进一步分类为CH活化（CHA）或CH氧化（CHO）。定义了这些各种分类的基础。特别地，CHA反应被定义为与甲烷发生的元素反应，该反应会生成离散的甲基中间体，其中碳上的形式氧化态（FOS）相对于甲烷而言处于-IV。相反，CHO反应被定义为与甲烷的基本反应，其中产物的碳原子被氧化，且FOS的负值小于-IV。这项审查表明，该领域的大部分工作相对平均地分布在所有分类的领域中。但是，仅对某些区域进行了边际检查，或者根本没有进行检查。这项审查还表明，尽管科学取得了重大进展，但取得了更大的进步，特别是在开发可以利用O的系统中参照图2，将需要开发可替代当前能源和资本密集型天然气转化过程的实用过程。我们相信，这种分类方案将为读者提供一种快速识别感兴趣的系统的方法，同时对甲烷功能化的广泛文献提供更深入的理解和理解，包括实际和基础知识。希望这可以加快实现这一“巨大挑战”的速度。
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