Unexpected isomerization of a cis- into a trans-Dihydride Complex. A neutral late transition metal complex as a hydride donor

Boris Rybtchinski, Yehoshoa Ben-David, David Milstein

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Abstract

Reaction of HIr(PPh3)3(CO) (1) with 1,3-bis[(diisopropylphosphino)methyl]benzene (2) in THF or benzene at 60 °C affords trans-H2Ir(CO)L (3; L = C6H3(CH2P(i-Pr2)2). The cationic complex [HIr(PPh3)(CO)L]Br (5) was obtained in the reaction of 1 with 1,3-bis[(diisopropylphosphino)methyl]-2-bromobenzene (4). Reaction of 5 with KO-t-Bu leads to the Ir(I) complex Ir(CO)L (6), which adds methyl iodide to form IIr(CO)(CH3)L (7). Addition of H2 to 6 results in formation of cis-(L)Ir(H)2CO) (8). This reaction is reversible, due to the rigid squareplanar geometry of 6. Under H2 pressure 8 isomerizes into 3, demonstrating cis- into trans-dihydride isomerization, which is unprecedented for octahedral complexes. The trans-dihydride six-coordinate complex 3 exhibits hydridic reactivity which is unusual for a neutral late transition metal complex and is due to the strong mutual irons influence of the hydride ligands. Various electrophiles ([Ph3C]BF4, PhC(O)Cl, CS2, MeI) directly attack the hydride ligand of 3, forming products of selective hydride transfer. Abstraction of the hydride ligand with the electrophiles affords the iridium complexes [HIr(PPh3)(CO)L]Br (9), HIr(Cl)(CO)L (10), HIr(CO)(SC(S)H)L (11), and HIr(I)(CO)L (12).

Original languageEnglish
Pages (from-to)3786-3793
Number of pages8
JournalOrganometallics
Volume16
Issue number17
Publication statusPublished - Aug 19 1997

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dihydrides
Coordination Complexes
Carbon Monoxide
Isomerization
Hydrides
isomerization
hydrides
Transition metals
transition metals
ligands
benzene
iridium
iodides
attack
Ligands
reactivity
iron
Iridium
products
geometry

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Unexpected isomerization of a cis- into a trans-Dihydride Complex. A neutral late transition metal complex as a hydride donor. / Rybtchinski, Boris; Ben-David, Yehoshoa; Milstein, David.

In: Organometallics, Vol. 16, No. 17, 19.08.1997, p. 3786-3793.

Research output: Contribution to journalArticle

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abstract = "Reaction of HIr(PPh3)3(CO) (1) with 1,3-bis[(diisopropylphosphino)methyl]benzene (2) in THF or benzene at 60 °C affords trans-H2Ir(CO)L (3; L = C6H3(CH2P(i-Pr2)2). The cationic complex [HIr(PPh3)(CO)L]Br (5) was obtained in the reaction of 1 with 1,3-bis[(diisopropylphosphino)methyl]-2-bromobenzene (4). Reaction of 5 with KO-t-Bu leads to the Ir(I) complex Ir(CO)L (6), which adds methyl iodide to form IIr(CO)(CH3)L (7). Addition of H2 to 6 results in formation of cis-(L)Ir(H)2CO) (8). This reaction is reversible, due to the rigid squareplanar geometry of 6. Under H2 pressure 8 isomerizes into 3, demonstrating cis- into trans-dihydride isomerization, which is unprecedented for octahedral complexes. The trans-dihydride six-coordinate complex 3 exhibits hydridic reactivity which is unusual for a neutral late transition metal complex and is due to the strong mutual irons influence of the hydride ligands. Various electrophiles ([Ph3C]BF4, PhC(O)Cl, CS2, MeI) directly attack the hydride ligand of 3, forming products of selective hydride transfer. Abstraction of the hydride ligand with the electrophiles affords the iridium complexes [HIr(PPh3)(CO)L]Br (9), HIr(Cl)(CO)L (10), HIr(CO)(SC(S)H)L (11), and HIr(I)(CO)L (12).",
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T1 - Unexpected isomerization of a cis- into a trans-Dihydride Complex. A neutral late transition metal complex as a hydride donor

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N2 - Reaction of HIr(PPh3)3(CO) (1) with 1,3-bis[(diisopropylphosphino)methyl]benzene (2) in THF or benzene at 60 °C affords trans-H2Ir(CO)L (3; L = C6H3(CH2P(i-Pr2)2). The cationic complex [HIr(PPh3)(CO)L]Br (5) was obtained in the reaction of 1 with 1,3-bis[(diisopropylphosphino)methyl]-2-bromobenzene (4). Reaction of 5 with KO-t-Bu leads to the Ir(I) complex Ir(CO)L (6), which adds methyl iodide to form IIr(CO)(CH3)L (7). Addition of H2 to 6 results in formation of cis-(L)Ir(H)2CO) (8). This reaction is reversible, due to the rigid squareplanar geometry of 6. Under H2 pressure 8 isomerizes into 3, demonstrating cis- into trans-dihydride isomerization, which is unprecedented for octahedral complexes. The trans-dihydride six-coordinate complex 3 exhibits hydridic reactivity which is unusual for a neutral late transition metal complex and is due to the strong mutual irons influence of the hydride ligands. Various electrophiles ([Ph3C]BF4, PhC(O)Cl, CS2, MeI) directly attack the hydride ligand of 3, forming products of selective hydride transfer. Abstraction of the hydride ligand with the electrophiles affords the iridium complexes [HIr(PPh3)(CO)L]Br (9), HIr(Cl)(CO)L (10), HIr(CO)(SC(S)H)L (11), and HIr(I)(CO)L (12).

AB - Reaction of HIr(PPh3)3(CO) (1) with 1,3-bis[(diisopropylphosphino)methyl]benzene (2) in THF or benzene at 60 °C affords trans-H2Ir(CO)L (3; L = C6H3(CH2P(i-Pr2)2). The cationic complex [HIr(PPh3)(CO)L]Br (5) was obtained in the reaction of 1 with 1,3-bis[(diisopropylphosphino)methyl]-2-bromobenzene (4). Reaction of 5 with KO-t-Bu leads to the Ir(I) complex Ir(CO)L (6), which adds methyl iodide to form IIr(CO)(CH3)L (7). Addition of H2 to 6 results in formation of cis-(L)Ir(H)2CO) (8). This reaction is reversible, due to the rigid squareplanar geometry of 6. Under H2 pressure 8 isomerizes into 3, demonstrating cis- into trans-dihydride isomerization, which is unprecedented for octahedral complexes. The trans-dihydride six-coordinate complex 3 exhibits hydridic reactivity which is unusual for a neutral late transition metal complex and is due to the strong mutual irons influence of the hydride ligands. Various electrophiles ([Ph3C]BF4, PhC(O)Cl, CS2, MeI) directly attack the hydride ligand of 3, forming products of selective hydride transfer. Abstraction of the hydride ligand with the electrophiles affords the iridium complexes [HIr(PPh3)(CO)L]Br (9), HIr(Cl)(CO)L (10), HIr(CO)(SC(S)H)L (11), and HIr(I)(CO)L (12).

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