A Study of the Interaction of some cationic Transition-Metal compounds with Carbon Monoxide and Nucleophiles
type: CreativeWork
description: A number of novel cationic carbonyl complexes of ruthenium and rhodium have been synthesised and characterised. The work also investigates the attack of nucleophiles on such species and examines the feasibility of these reactions as a possible first step in the catalytic production of organic esters. Mono and dipositive species of ruthenium have been effectively prepared by the reaction of [RuCl 2 (CO) 2{PPh3) 2 ] with AgBF4. The cationic 2species [RuCl(CO) 2 (PPh3) 2 ] [BF4 ] . 1/2(CH2C1 2 ) and [Ru(CO) 2 (PPh3) 2 ] [BF4] 22£H2cl2jiave been prepared under nitrogea The compound [Ru(CO)3(PPh3)2] [BF4 ] 2 has been synthesised in the presence of CO. The compound, [RuCl(CO)2(PPh3)2] [BF4 ] . l/2(CH2Cl2) reacts with 0*30 under CO to give [RuCl(COOCH3J I (00)2^*13)2. The compounds [Ru(CO) 2 (PPh3 ) 2 r [BF4 ] 2.CH2C1 2 and [Ru(CO) 3 (PPh3 ) 2 ] [BP4 ] 2 effectively form cis-[Ru(COOCH3)2(CO)2(PPh3)2] by the reaction of CHsONa in the presence of CO at room temperature. This dialkoxycarbonyl compound preparation from the dipositive species are energetically more favourable than the cis-[RuCl2(CO)2(PPh3)2L where the2reaction takes place at CO high pressure. The compound [Ru(CO)2(PPh3)2] [BF4 ] 2. CH2C1 2 reacts with NaBH4, Nal, cone. HC1 and CHsCOONa to give the dihydrido, diiodo, dichloro and bisethanoato compounds respectively. Cationic complexes of rhodium have been synthesised by the reaction of trans-[RhCl(CO)(L)2], (L = PPhs, AsPhs, PCys) with AgBF4 in the absence and presence of CO to give [Rh(CO|(L)2]_[BF4]~. n CH2C12 [where n = 1/2 or 3/2] and trans- [Rh(CO) 2 (L) 2 ] [BF4J~ respectively. These cations react with PONa (R = CH3/ C2Hs) to give [Rh(OR) (CO) (L) 2 ] and [Rh(COOR)(CO)(L) 2 ], (R = CH3, L = PPh3/ PCy3 ). The alkoxycarbonyl compound, [Rh(COOR) (CO) 2 (L) 2 ] is formed by the reaction of sodium alkoxide in the presence of CO, (when R = CH3, C2Hs, C3H7, then L = PPh3 and when R = CH3 then L = AsPh3). The alkoxo compound, Rh(OCH3) (CO) (L) 2, (L = PPh3 ) oxida…
abstract: A number of novel cationic carbonyl complexes of ruthenium and rhodium have been synthesised and characterised. The work also investigates the attack of nucleophiles on such species and examines the feasibility of these reactions as a possible first step in the catalytic production of organic esters. Mono and dipositive species of ruthenium have been effectively prepared by the reaction of [RuCl 2 (CO) 2{PPh3) 2 ] with AgBF4. The cationic 2species [RuCl(CO) 2 (PPh3) 2 ] [BF4 ] . 1/2(CH2C1 2 ) and [Ru(CO) 2 (PPh3) 2 ] [BF4] 22£H2cl2jiave been prepared under nitrogea The compound [Ru(CO)3(PPh3)2] [BF4 ] 2 has been synthesised in the presence of CO. The compound, [RuCl(CO)2(PPh3)2] [BF4 ] . l/2(CH2Cl2) reacts with 0*30 under CO to give [RuCl(COOCH3J I (00)2^*13)2. The compounds [Ru(CO) 2 (PPh3 ) 2 r [BF4 ] 2.CH2C1 2 and [Ru(CO) 3 (PPh3 ) 2 ] [BP4 ] 2 effectively form cis-[Ru(COOCH3)2(CO)2(PPh3)2] by the reaction of CHsONa in the presence of CO at room temperature. This dialkoxycarbonyl compound preparation from the dipositive species are energetically more favourable than the cis-[RuCl2(CO)2(PPh3)2L where the2reaction takes place at CO high pressure. The compound [Ru(CO)2(PPh3)2] [BF4 ] 2. CH2C1 2 reacts with NaBH4, Nal, cone. HC1 and CHsCOONa to give the dihydrido, diiodo, dichloro and bisethanoato compounds respectively. Cationic complexes of rhodium have been synthesised by the reaction of trans-[RhCl(CO)(L)2], (L = PPhs, AsPhs, PCys) with AgBF4 in the absence and presence of CO to give [Rh(CO|(L)2]_[BF4]~. n CH2C12 [where n = 1/2 or 3/2] and trans- [Rh(CO) 2 (L) 2 ] [BF4J~ respectively. These cations react with PONa (R = CH3/ C2Hs) to give [Rh(OR) (CO) (L) 2 ] and [Rh(COOR)(CO)(L) 2 ], (R = CH3, L = PPh3/ PCy3 ). The alkoxycarbonyl compound, [Rh(COOR) (CO) 2 (L) 2 ] is formed by the reaction of sodium alkoxide in the presence of CO, (when R = CH3, C2Hs, C3H7, then L = PPh3 and when R = CH3 then L = AsPh3). The alkoxo compound, Rh(OCH3) (CO) (L) 2, (L = PPh3 ) oxida…
author: Howlader, M. B. H.
language: eng
date published: 1993-1
date modified: 2026-07-24T04:39:18Z
provider: University of South Wales
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: University of South Wales