Synthesis, structures, and reactions of manganese complexes containing diphosphine ligands with pendant amines

Kevin D. Welch, William G. Dougherty, W. Scott Kassel, Daniel L DuBois, R Morris Bullock

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Abstract

Addition of the pendant amine ligand PNRP (PNRP = Ph2PCH2NRCH2PPh2; R = Me, Ph, n-Bu) to Mn(CO)5Br gives fac-Mn(PNRP)(CO)3Br. Photolysis of fac-Mn(PNRP)(CO)3Br with dppm [dppm = 1,2-bis(diphenylphosphino)methane] provides mixed bis(diphosphine) complexes, trans-Mn(PNRP)(dppm)(CO)(Br). Reaction of trans-Mn(PN RP)(dppm)(CO)(Br) with LiAlH4 leads to trans-Mn(PN RP)(dppm)(CO)(H), which has been characterized by crystallography. Mn(P2 PhN2 Bn)(dppm)(CO)(H) [P 2 PhN2 Bn = 1,5-diphenyl-3,7-dibenzyl- 1,5-diaza-3,7-diphosphacyclooctane] can be prepared in a similar manner; its structure has one chelate ring in a chair conformation and the second in a boat conformation. The boat-conformer ring directs the nitrogen of the ring toward the carbonyl ligand, and the N⋯C distance between one N of the P 2 PhN2 Bn ligand and CO is 3.171(4) Å, indicating a weak interaction between the N of the pendant amine and the CO ligand. Reaction of NaBArF 4 (ArF = 3,5-bis(trifluoromethyl)phenyl) with Mn(P-P)(dppm)(CO)(Br) produces the cations [Mn(P-P)(dppm)(CO)]+. The crystal structure of [Mn(PN MeP)(dppm)(CO)][BArF 4] shows two very weak agostic interactions between C-H bonds on the phenyl ring and the Mn. The cationic complexes [Mn(P-P)(dppm)(CO)]+ react with H2 to form dihydrogen complexes [Mn(H2)(P-P)(dppm)(CO)]+ (K eq = 1-90 atm-1 in fluorobenzene, for a series of different P-P ligands). Similar equilibria with N2 produce [Mn(N 2)(P-P)(dppm)(CO)]+ (Keq generally 1-3.5 atm-1 in fluorobenzene).

Original languageEnglish
Pages (from-to)4532-4540
Number of pages9
JournalOrganometallics
Volume29
Issue number20
DOIs
Publication statusPublished - Oct 25 2010

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Carbon Monoxide
Manganese
Amines
manganese
amines
Ligands
ligands
synthesis
rings
boats
Fluorobenzenes
chelates
seats
crystallography
photolysis
methane
Boats
nitrogen
cations
crystal structure

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Synthesis, structures, and reactions of manganese complexes containing diphosphine ligands with pendant amines. / Welch, Kevin D.; Dougherty, William G.; Kassel, W. Scott; DuBois, Daniel L; Bullock, R Morris.

In: Organometallics, Vol. 29, No. 20, 25.10.2010, p. 4532-4540.

Research output: Contribution to journalArticle

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abstract = "Addition of the pendant amine ligand PNRP (PNRP = Ph2PCH2NRCH2PPh2; R = Me, Ph, n-Bu) to Mn(CO)5Br gives fac-Mn(PNRP)(CO)3Br. Photolysis of fac-Mn(PNRP)(CO)3Br with dppm [dppm = 1,2-bis(diphenylphosphino)methane] provides mixed bis(diphosphine) complexes, trans-Mn(PNRP)(dppm)(CO)(Br). Reaction of trans-Mn(PN RP)(dppm)(CO)(Br) with LiAlH4 leads to trans-Mn(PN RP)(dppm)(CO)(H), which has been characterized by crystallography. Mn(P2 PhN2 Bn)(dppm)(CO)(H) [P 2 PhN2 Bn = 1,5-diphenyl-3,7-dibenzyl- 1,5-diaza-3,7-diphosphacyclooctane] can be prepared in a similar manner; its structure has one chelate ring in a chair conformation and the second in a boat conformation. The boat-conformer ring directs the nitrogen of the ring toward the carbonyl ligand, and the N⋯C distance between one N of the P 2 PhN2 Bn ligand and CO is 3.171(4) {\AA}, indicating a weak interaction between the N of the pendant amine and the CO ligand. Reaction of NaBArF 4 (ArF = 3,5-bis(trifluoromethyl)phenyl) with Mn(P-P)(dppm)(CO)(Br) produces the cations [Mn(P-P)(dppm)(CO)]+. The crystal structure of [Mn(PN MeP)(dppm)(CO)][BArF 4] shows two very weak agostic interactions between C-H bonds on the phenyl ring and the Mn. The cationic complexes [Mn(P-P)(dppm)(CO)]+ react with H2 to form dihydrogen complexes [Mn(H2)(P-P)(dppm)(CO)]+ (K eq = 1-90 atm-1 in fluorobenzene, for a series of different P-P ligands). Similar equilibria with N2 produce [Mn(N 2)(P-P)(dppm)(CO)]+ (Keq generally 1-3.5 atm-1 in fluorobenzene).",
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T1 - Synthesis, structures, and reactions of manganese complexes containing diphosphine ligands with pendant amines

AU - Welch, Kevin D.

AU - Dougherty, William G.

AU - Kassel, W. Scott

AU - DuBois, Daniel L

AU - Bullock, R Morris

PY - 2010/10/25

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N2 - Addition of the pendant amine ligand PNRP (PNRP = Ph2PCH2NRCH2PPh2; R = Me, Ph, n-Bu) to Mn(CO)5Br gives fac-Mn(PNRP)(CO)3Br. Photolysis of fac-Mn(PNRP)(CO)3Br with dppm [dppm = 1,2-bis(diphenylphosphino)methane] provides mixed bis(diphosphine) complexes, trans-Mn(PNRP)(dppm)(CO)(Br). Reaction of trans-Mn(PN RP)(dppm)(CO)(Br) with LiAlH4 leads to trans-Mn(PN RP)(dppm)(CO)(H), which has been characterized by crystallography. Mn(P2 PhN2 Bn)(dppm)(CO)(H) [P 2 PhN2 Bn = 1,5-diphenyl-3,7-dibenzyl- 1,5-diaza-3,7-diphosphacyclooctane] can be prepared in a similar manner; its structure has one chelate ring in a chair conformation and the second in a boat conformation. The boat-conformer ring directs the nitrogen of the ring toward the carbonyl ligand, and the N⋯C distance between one N of the P 2 PhN2 Bn ligand and CO is 3.171(4) Å, indicating a weak interaction between the N of the pendant amine and the CO ligand. Reaction of NaBArF 4 (ArF = 3,5-bis(trifluoromethyl)phenyl) with Mn(P-P)(dppm)(CO)(Br) produces the cations [Mn(P-P)(dppm)(CO)]+. The crystal structure of [Mn(PN MeP)(dppm)(CO)][BArF 4] shows two very weak agostic interactions between C-H bonds on the phenyl ring and the Mn. The cationic complexes [Mn(P-P)(dppm)(CO)]+ react with H2 to form dihydrogen complexes [Mn(H2)(P-P)(dppm)(CO)]+ (K eq = 1-90 atm-1 in fluorobenzene, for a series of different P-P ligands). Similar equilibria with N2 produce [Mn(N 2)(P-P)(dppm)(CO)]+ (Keq generally 1-3.5 atm-1 in fluorobenzene).

AB - Addition of the pendant amine ligand PNRP (PNRP = Ph2PCH2NRCH2PPh2; R = Me, Ph, n-Bu) to Mn(CO)5Br gives fac-Mn(PNRP)(CO)3Br. Photolysis of fac-Mn(PNRP)(CO)3Br with dppm [dppm = 1,2-bis(diphenylphosphino)methane] provides mixed bis(diphosphine) complexes, trans-Mn(PNRP)(dppm)(CO)(Br). Reaction of trans-Mn(PN RP)(dppm)(CO)(Br) with LiAlH4 leads to trans-Mn(PN RP)(dppm)(CO)(H), which has been characterized by crystallography. Mn(P2 PhN2 Bn)(dppm)(CO)(H) [P 2 PhN2 Bn = 1,5-diphenyl-3,7-dibenzyl- 1,5-diaza-3,7-diphosphacyclooctane] can be prepared in a similar manner; its structure has one chelate ring in a chair conformation and the second in a boat conformation. The boat-conformer ring directs the nitrogen of the ring toward the carbonyl ligand, and the N⋯C distance between one N of the P 2 PhN2 Bn ligand and CO is 3.171(4) Å, indicating a weak interaction between the N of the pendant amine and the CO ligand. Reaction of NaBArF 4 (ArF = 3,5-bis(trifluoromethyl)phenyl) with Mn(P-P)(dppm)(CO)(Br) produces the cations [Mn(P-P)(dppm)(CO)]+. The crystal structure of [Mn(PN MeP)(dppm)(CO)][BArF 4] shows two very weak agostic interactions between C-H bonds on the phenyl ring and the Mn. The cationic complexes [Mn(P-P)(dppm)(CO)]+ react with H2 to form dihydrogen complexes [Mn(H2)(P-P)(dppm)(CO)]+ (K eq = 1-90 atm-1 in fluorobenzene, for a series of different P-P ligands). Similar equilibria with N2 produce [Mn(N 2)(P-P)(dppm)(CO)]+ (Keq generally 1-3.5 atm-1 in fluorobenzene).

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