Two hybrid materials (1_TiO₂ and 2_TiO₂) were designed and prepared by anchoring novel [Cp*Ir(κ³‐O,N,O‐glyphosate)] (1; glyphosate=N‐(phosphonomethyl)glycine) and [Cp*Ir(κ³‐O,N,O‐glyphosine)] (2; glyphosine=N,N‐bis(phosphonomethyl)glycine) complexes onto rutile TiO₂. Characterization in solution (NMR spectroscopy) and solid state (X‐Ray diffractometry) indicates that 1 and 2 are stabilized by the two arms of the glycine fragment, whereas they have (2) or can easily generate (1 and 2) a dandling phosphonate arm suitable for their anchoring on TiO₂. As a matter of fact, they exhibit rather elongated Ir–OP (1: 2.1405 Å, 2: 2.142 Å) and short Ir–OC (1: 2.0784 Å, 2: 2.086 Å) and Ir–N (1: 2.155 Å, 2: 2.207 Å) bonds. NMR spectra of 2 show a dynamic process that exchanges the two phosphonate moieties, consistently with an easy –OP detachment from Ir. Both molecular and heterogenized species were tested as catalysts in water oxidation (WO) driven by NaIO₄. 1 (TOF up to 96 min⁻¹) and 2 (26 min⁻¹) proved to be effective molecular catalysts; more importantly, 1_TiO₂ and 2_TiO₂ showed very high activity (TOF ∼200 min⁻¹), which remained rather constant over seven successive runs, even if substantial leaching of the noble metal in solution occurred during the first catalytic tests. TON was very high and limited only by the amount of NaIO₄ used. These results show the potentialities of mixed carboxylate/phosphonate ligands for the development of highly active water oxidation catalysts.

中文翻译：

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草甘膦和草甘膦作为辅助和固定配体的分子和异构Cp * Ir水氧化催化剂

两个杂化材料（1_TiO ₂和2_TiO ₂）设计并通过锚定新颖制备的[Cp *铱（κ ³ -O，N，O-草甘膦）]（1 ;草甘膦= N-（膦酰基甲基）甘氨酸）和的[Cp * IR（κ ³ -O，N，O-草甘）]（2 ;草甘= N，N-双（膦酰基甲基）甘氨酸）配合到金红石型二氧化钛₂。溶液（NMR光谱）和固态（X射线衍射）的表征表明1和2由甘氨酸片段的两个臂稳定，而它们具有（2）或易于生成（1和2）适合锚固在TiO ₂上的膦酸酯臂。事实上，它们的Ir-OP（1：2.1405Å，2：2.142Å）相当长，Ir-OC（1：2.0784Å，2：2.086Å ）和Ir–N（1：2.155Å，2：2.207Å）键。2的NMR谱图显示了一个动态过程，该过程交换了两个膦酸酯部分，并与Ir发生了简单的–OP分离。分子和异质物种均被测试为NaIO ₄驱动的水氧化（WO）的催化剂。1（TOF长达96分钟^-1）和2（26分钟^-1）被证明是有效的分子催化剂；更重要的是1_TiO ₂和2_TiO ₂表现出很高的活性（TOF〜200 min ^-1），即使在第一次催化测试中发生了溶液中贵金属的大量浸出，在连续七个连续运行中仍保持相当稳定。TON非常高，仅受NaIO ₄用量的限制。这些结果表明混合的羧酸盐/膦酸盐配体在开发高活性水氧化催化剂方面的潜力。