Synthesis, Chemistry, and Catalytic Activity of Ruthenium Diaminodiphosphane Complexes − Crystal Structures of <I>trans</I>-[RuCl<INF>2</INF>{<I>κ</I><SUP>3</SUP>-Ph<INF>2</INF>PC<INF>6</INF>H<INF>4</INF>CH=NC<INF>6</INF>H<INF>10</INF>N(H)CH<INF>2</INF>C<INF>6</INF>H<INF>4</INF>PPh<INF>2</INF>}(PPh<INF>3</INF>)] and <I>cis</I>-[RuCl<INF>2</INF>{<I>κ</I><SUP>4</SUP>-Ph<INF>2</INF>PC<INF>6</INF>H<INF>4</INF>CH=NC<INF>6</INF>H<INF>10</INF>N(H)CH<INF>2</INF>C<INF>6</INF>H<INF>4</INF>PPh<INF>2</INF>}]

Wai-Kwok, W; Xiao-Ping, C; Wei-Xiong, P; Jian-Ping, G; Wai-Yeung, W

HERO ID

995052

Reference Type

Journal Article

Year

2002

HERO ID 995052
In Press No
Year 2002
Title Synthesis, Chemistry, and Catalytic Activity of Ruthenium Diaminodiphosphane Complexes − Crystal Structures of <I>trans</I>-[RuCl<INF>2</INF>{<I>κ</I><SUP>3</SUP>-Ph<INF>2</INF>PC<INF>6</INF>H<INF>4</INF>CH=NC<INF>6</INF>H<INF>10</INF>N(H)CH<INF>2</INF>C<INF>6</INF>H<INF>4</INF>PPh<INF>2</INF>}(PPh<INF>3</INF>)] and <I>cis</I>-[RuCl<INF>2</INF>{<I>κ</I><SUP>4</SUP>-Ph<INF>2</INF>PC<INF>6</INF>H<INF>4</INF>CH=NC<INF>6</INF>H<INF>10</INF>N(H)CH<INF>2</INF>C<INF>6</INF>H<INF>4</INF>PPh<INF>2</INF>}]
Authors Wai-Kwok, W; Xiao-Ping, C; Wei-Xiong, P; Jian-Ping, G; Wai-Yeung, W
Journal European Journal of Inorganic Chemistry
Volume 2002
Page Numbers 231
Abstract The interaction of [RuCl<INF>2</INF>(PPh<INF>3</INF>)<INF>3</INF>] with one equivalent of <I>N</I>,<I>N</I>'-bis[2-(diphenylphosphanyl)benzyl]-1<I>R</I>,2<I>R</I>-cyclohexanediamine [1<I>R</I>,2<I>R</I>-P(NH)(NH)P] in dichloromethane at room temperature gave <I>trans</I>-[RuCl<INF>2</INF>{<I>κ</I><SUP>3</SUP>-1<I>R</I>,2<I>R</I>-P(NH)(NH)P}(PPh<INF>3</INF>)] (<B>1</B>). When heated under reflux in toluene under a nitrogen atmosphere, <B>1</B> was converted into <I>trans</I>-[RuCl<INF>2</INF>{<I>κ</I><SUP>4</SUP>-1<I>R</I>,2<I>R</I>-P(NH)(NH)P}] (<B>2</B>). However, when <B>1</B> was stirred at room temperature in air, it was oxidized to <I>trans</I>-[RuCl<INF>2</INF>{<I>κ</I><SUP>3</SUP>-1<I>R</I>,2<I>R</I>-PN(NH)P}(PPh<INF>3</INF>)] (<B>3</B>). Depending on the reaction conditions, <B>3</B> was converted into <I>trans</I>-[RuCl<INF>2</INF>{<I>κ</I><SUP>3</SUP>-1<I>R</I>,2<I>R</I>-P(NH)(NH)P=O}(PPh<INF>3</INF>)] (<B>4</B>) when heated to 80 °C in toluene in air, to <I>cis</I>-[RuCl<INF>2</INF>{<I>κ</I><SUP>4</SUP>-1<I>R</I>,2<I>R</I>-PN(NH)P}] (<B>5</B>) when stirred at room temperature in acetone in air, or to <I>trans</I>-[RuCl<INF>2</INF>{<I>κ</I><SUP>4</SUP>-1<I>R</I>,2<I>R</I>-PN(NH)P}] (<B>6</B>) when heated under reflux in acetone under a nitrogen atmosphere. When heated under reflux in toluene under a nitrogen atmosphere, <B>5</B> isomerized to <B>6</B> quantitatively. When heated under reflux in mesitylene under a nitrogen atmosphere, <B>6</B> was slowly reduced to <B>2</B>. The solid state structures of <B>3</B> and <B>5</B> were ascertained by X-ray crystallography. Catalytic studies showed that <B>1</B> could catalyze the oxidation of alkanes and alkenes with molecular oxygen.
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