2021
DOI: 10.1021/acs.organomet.1c00603
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Activation of H2 with Dinuclear Manganese(I)-Phosphido Complexes

Abstract: There are few reports of activation of H2 across metal–phosphido linkages, and all of the first-row metal examples use N-heterocyclic phosphido donors. In this report, we highlight the discovery of H2 activation using first-row transition-metal phosphido complexes with alkyl and aryl substituents. The complex [Mn­(CO)4(μ-PPh2)]2 (1) was treated with H2 (125 °C, 33 h), affording [{Mn­(CO)4}­(μ-H)­(μ-PPh2)­{Mn­(CO)3(Ph2PH)}] (2). Treating 2 with Mn2(CO)10 leads to PH bond activation and formation of [{Mn­(CO)4}­… Show more

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Cited by 7 publications
(37 citation statements)
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“…The reaction of 2 with equimolar dpa in toluene‐ d 8 was monitored over various temperatures. The reaction was slow at 80 °C and mostly contained unreacted 2 (>90 %) even after 44 h. The products were identified as [{Mn(CO) 4 }( μ ‐H)( μ ‐P( i Pr) 2 ){Mn(CO) 3 ( κ‐P‐ hpa )}] ( 5 ), [Mn 2 (CO) 9 { κ‐P ‐ hpa }] ( 7 ), [{Mn(CO) 4 }( μ ‐H)( μ ‐P( i Pr) 2 ){Mn(CO) 3 (HP( i Pr) 2 )}] ( 8 ), [28] and Mn 2 (CO) 10 owing to the presence of 8 [28] . Further heating to 105 °C (12 h) caused the disappearance of 8 and the growth of 5 and 7 in addition to the formation of a new mononuclear Mn hydride complex fac ‐Mn(CO) 3 (H)( κ 2 ‐P ‐η 2 ‐ hpa ) ( 4 ).…”
Section: Resultsmentioning
confidence: 99%
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“…The reaction of 2 with equimolar dpa in toluene‐ d 8 was monitored over various temperatures. The reaction was slow at 80 °C and mostly contained unreacted 2 (>90 %) even after 44 h. The products were identified as [{Mn(CO) 4 }( μ ‐H)( μ ‐P( i Pr) 2 ){Mn(CO) 3 ( κ‐P‐ hpa )}] ( 5 ), [Mn 2 (CO) 9 { κ‐P ‐ hpa }] ( 7 ), [{Mn(CO) 4 }( μ ‐H)( μ ‐P( i Pr) 2 ){Mn(CO) 3 (HP( i Pr) 2 )}] ( 8 ), [28] and Mn 2 (CO) 10 owing to the presence of 8 [28] . Further heating to 105 °C (12 h) caused the disappearance of 8 and the growth of 5 and 7 in addition to the formation of a new mononuclear Mn hydride complex fac ‐Mn(CO) 3 (H)( κ 2 ‐P ‐η 2 ‐ hpa ) ( 4 ).…”
Section: Resultsmentioning
confidence: 99%
“…( i ) First, the alkyne reacts with 2 via a ligand substitution reaction to form 11 . The stereochemistry of 11 can take many forms based on the known substitution chemistry with 2 , 5 and 8 and other related analogs [5,28,50] . The isomer given is the lowest energy isomer obtained from DFT calculations (Figures 5 and S51).…”
Section: Resultsmentioning
confidence: 99%
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