Unsymmetric Ir2 and RhIr Dinuclear Complexes Supported by a Linear Tetraphosphine meso-dpmppp, Showing High Reactivity for O2, H2, and HCl
Year: 2024
Type: article
Abstract: Unsymmetric dinuclear Ir(I) complexes, [Ir 2 Cl 2 (L)( meso -dpmppp)] (L = XylNC ( 1aIr 2 ), t BuNC ( 1bIr 2 ), CO ( 1cIr 2 )), were synthesized using meso -Ph 2 PCH 2 P(Ph)(CH 2 ) 3 P(Ph)CH 2 PPh 2 ( meso -dpmppp), which supports cis - P,P (M 1 ) and trans-P,P (M 2 ) metal sites, and exhibited high reactivity for O 2, H 2, and HCl. The IrRh heterodinuclear complexes, [M 1 M 2 Cl 2 (L)( meso -dpmppp)] ( 1 x M 1 M 2 ) (M 1 M 2 = IrRh, RhIr; L = XylNC, CO ( x = a, c )), were also synthesized and used together with the Rh 2 complexes ( 1a,cRh 2 ) to elucidate the role of each metal site. For the reactions of O 2, 1aIr 2 and 1aRhIr showed higher reactivity than those of 1aIrRh and 1aRh 2, giving η 2 –peroxide complexes [{M 1 Cl 2 }{M 2 (η 2 –O 2 )(XylNC)}( meso -dpmppp)] ( 2aIr 2, 2aRhIr ), from which O 2 would not dissociate. All the CO complexes 1cM 1 M 2 (M 1, M 2 = Ir or Rh) showed no reactivity for O 2 . In the reactions with H 2, 1aIr 2 reacted with H 2 to give the dihydride complex, [{IrCl 2 }{Ir(H) 2 L}( meso -dpmppp)] ( 11aIr 2 ) and the tetrahydride complex, [{Ir(H)Cl 2 }(μ–H){Ir(H) 2 L}( meso -dpmppp)] ( 12aIr 2 ), while 1aRhIr gave the dihydride complex, and 1aIrRh and 1aRh 2 gave no hydride complexes. Reactions of 1a,cM 1 M 2 with HCl afforded the dihydride complexes, [{IrCl 3 }(μ–H){Ir(H)Cl(XylNC)}( meso -dpmppp)] ( 14aIr 2 ), [{Ir(H)Cl 2 }(μ–H){M 2 Cl 2 (L)}( meso -dpmppp)] (M 2 = Ir, L = CO ( 15cIr 2 ); M 2 = Rh, L = XylNC ( 15aIrRh ), CO ( 15cIrRh )), and [{Rh(H)Cl 2 }(μ–Cl){Ir(H)Cl(XylNC)}( meso -dpmppp)] ( 18aRhIr ), the structures varying depending on M 1 and M 2 as well as L.
Source: Inorganic Chemistry
Institution: Nara Women's University
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
OpenAlex ID: W4403209591