磷酸乙酯钠作为磷源合成分子磷化铑的探索性研究

IF 3.3 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions Pub Date : 2025-09-26 DOI:10.1039/d5dt02274f

Jaap E Borger, Fabian Müller, Peter Coburger, Hansjörg Grützmacher, Zhongshu Li, Thomas L. Gianetti, Bruno Pribanic

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引用次数: 0

摘要

含有Rh2P2和前所未有的Rh4P4核的分子过渡金属磷化物（TMPs）可以由Na[OCP]和铑(I)前体配合物携带双螯合tropPPh2配体生成。这些反应通过正式的p转移步骤（trop = 5h -二苯并[a，d]环庚烯-5-基）进行，这涉及CO单元向Rh(I)中心的迁移。与相关的四齿配体trop3P和三齿配体trop2PPh一起，第一个中性和阴离子[Rhx(L)n(PCO)y]z配合物含有多达两个铑中心和三个完整的磷酸乙酯单元。这些配合物对CO的迁移是惰性的。结果表明，金属配位球对产物的形成有较大的影响，表明以Na[OCP]为p源制备RhP配合物最有效的是低配位铑(I)前驱体。

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Sodium phosphaethynolate as P-source for the synthesis of molecular rhodium phosphides: an exploratory study

Molecular transition metal phosphides (TMPs) containing a Rh2P2 and unprecedented Rh4P4 core could be generated from Na[OCP] and rhodium(I) precursor complexes carrying the bischelating tropPPh2 ligand. These reaction proceed through a formal P-transfer step (trop = 5H-dibenzo[a,d]cyclohepten-5-yl), which involves migration of the CO unit to the Rh(I) center. With the related tetradentate ligand trop3P and tridentate ligand trop2PPh the first neutral and anionic [Rhx(L)n(PCO)y]z complexes containing up to two rhodium centers and three intact phosphaethynolate units. These complexes are inert against CO migration. The results demonstrate a large influence of the metal coordination sphere on product formation, and indicate that low-coordinate rhodium(I) precursors are most effective for the preparation of RhP complexes using Na[OCP] as P-source.

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来源期刊

Dalton Transactions 化学-无机化学与核化学

CiteScore

6.60

自引率

7.50%

发文量

1832

审稿时长

1.5 months

期刊介绍： Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.