10.1021/ic020029z.s003
Matthew D. Hargreaves
Matthew D.
Hargreaves
Mary F. Mahon
Mary F.
Mahon
Michael K. Whittlesey
Michael K.
Whittlesey
Substitution Reactions of [Ru(dppe)(CO)(H<sub>2</sub>O)<sub>3</sub>][OTf]<sub>2</sub>
American Chemical Society
2002
Ru
Ph 2 PCH 2 CH 2 PPh 2
CN
water gas shift reaction
bpy
SCH
dimethyl sulfoxide results
CO
CH 3 CH 2 CH 2 SH
OTf
CNC
OSO 2 CF 3
6 b
2002-05-16 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Substitution_Reactions_of_Ru_dppe_CO_H_sub_2_sub_O_sub_3_sub_OTf_sub_2_sub_/3605499
The labile nature of the coordinated water ligands in the organometallic aqua complex [Ru(dppe)(CO)(H<sub>2</sub>O)<sub>3</sub>][OTf]<sub>2</sub>
(<b>1</b>) (dppe = Ph<sub>2</sub>PCH<sub>2</sub>CH<sub>2</sub>PPh<sub>2</sub>; OTf = OSO<sub>2</sub>CF<sub>3</sub>) has been investigated through substitution reactions with a
range of incoming ligands. Dissolution of <b>1</b> in acetonitrile or dimethyl sulfoxide results in the facile displacement of
all three waters to give [Ru(dppe)(CO)(CH<sub>3</sub>CN)<sub>3</sub>][OTf]<sub>2</sub> (<b>2</b>) and [Ru(dppe)(CO)(DMSO)<sub>3</sub>][OTf]<sub>2</sub> (<b>3</b>), respectively.
Similarly, <b>1</b> reacts with Me<sub>3</sub>CNC to afford [Ru(dppe)(CO)(CNCMe<sub>3</sub>)<sub>3</sub>][OTf]<sub>2</sub> (<b>4</b>). Addition of 1 equiv of 2,2‘-bipyridyl
(bpy) or 4,4‘-dimethyl-2,2‘-bipyridyl (Me<sub>2</sub>bpy) to acetone/water solutions of <b>1</b> initially yields [Ru(dppe)(CO)(H<sub>2</sub>O)(bpy)][OTf]<sub>2</sub> (<b>5a</b>) and [Ru(dppe)(CO)(H<sub>2</sub>O)(Me<sub>2</sub>bpy)][OTf]<sub>2</sub> (<b>6a</b>), in which the coordinated water lies trans to CO.
Compounds <b>5a</b> and <b>6a</b> rapidly rearrange to isomeric species (<b>5b</b>, <b>6b</b>) in which the ligated water is trans to dppe.
Further reactivity has been demonstrated for <b>6b</b>, which, upon dissolution in CDCl<sub>3</sub>, loses water and coordinates a
triflate anion to afford [Ru(dppe)(CO)(OTf)(Me<sub>2</sub>bpy)][OTf] (<b>7</b>). Reaction of <b>1</b> with CH<sub>3</sub>CH<sub>2</sub>CH<sub>2</sub>SH gives the dinuclear
bridging thiolate complex [{(dppe)Ru(CO)}<sub>2</sub>(μ-SCH<sub>2</sub>CH<sub>2</sub>CH<sub>3</sub>)<sub>3</sub>][OTf] (<b>8</b>). The reaction of <b>1</b> with CO in acetone/water is slow and yields the cationic hydride complex [Ru(dppe)(CO)<sub>3</sub>H][OTf] (<b>9</b>) via a water gas shift reaction.
Moreover, the same mechanism can also be used to account for the previously reported synthesis of <b>1</b> upon
reaction of Ru(dppe)(CO)<sub>2</sub>(OTf)<sub>2</sub> with water (<i>Organometallics</i> <b>1999</b>, <i>18</i>, 4068).