2020
DOI: 10.1002/chem.202002957
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The Butterfly Complex [{Cp*Cr(CO)3}2(μ,η1:1‐P4)] as a Versatile Ligand and Its Unexpected P1/P3 Fragmentation

Abstract: The versatile coordination behavior of the P4 butterfly complex [{Cp*Cr(CO)3}2(μ,η1:1‐P4)] (1) towards Lewis acidic pentacarbonyl compounds of Cr, Mo and W is reported. The reaction of 1 with [W(CO)4(nbd)] (nbd=norbornadiene) yields the complex [{Cp*Cr(CO)3}2(μ3,η1:1:1:1‐P4){W(CO)4}] (2) in which 1 serves as a chelating P4 butterfly ligand. In contrast, reactions of 1 with [M(CO)4(nbd)] (M=Cr (a), Mo (b)) result in the step‐wise formation of [{Cp*Cr(CO)2}2(μ3,η3:1:1‐P4){M(CO)5}] (3 a,b) and [{Cp*Cr(CO)2}2‐(μ4,… Show more

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Cited by 13 publications
(3 citation statements)
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“…The same reaction outcome, namely the formation of 5 , can be observed when isolated 4 is heated to 70 °C in n -hexane for 2 h. This strongly indicates that 5 is formed from 4 . A similar rearrangement of a P 4 -butterfly core has been reported for the reaction of [(Cp*Cr(CO) 3 } 2 (µ,η 1:1 -P 4 )] with [(Cr(CO) 4 (nbd)] (nbd = norbornadiene) [ 35 ]. In 2 , 3 and 4 , the As 4 ligand in 1 serves as a four-valence electron donor, while, in 5 , it serves as a six-electron donor.…”
Section: Resultssupporting
confidence: 66%
“…The same reaction outcome, namely the formation of 5 , can be observed when isolated 4 is heated to 70 °C in n -hexane for 2 h. This strongly indicates that 5 is formed from 4 . A similar rearrangement of a P 4 -butterfly core has been reported for the reaction of [(Cp*Cr(CO) 3 } 2 (µ,η 1:1 -P 4 )] with [(Cr(CO) 4 (nbd)] (nbd = norbornadiene) [ 35 ]. In 2 , 3 and 4 , the As 4 ligand in 1 serves as a four-valence electron donor, while, in 5 , it serves as a six-electron donor.…”
Section: Resultssupporting
confidence: 66%
“…Related transition-metal mediated [3+1] fragmentations of P4 have rarely been reported in the literature. 40,[44][45][46] To the best of our knowledge, our system is the first which incorporates both the resulting P3 and P1 fragment in the same product.…”
Section: Reactivity Studies Of Complex [K(18-c-6)(thf)][rac-1]mentioning
confidence: 99%
“…In most of the cases, the coordination of the "wing tip" phosphorus atoms of the intact butterfly to the electron-poor metal centre is observed, but also a rearrangement to a cyclo -P 4 unit. The complex [{Cp*Cr(CO) 3 } 2 (µ,η 1:1 -P 4 )] (Cp* = C 5 (CH 3 ) 5 ), which is similar to 1 , isomerizes in reactions with M(CO) 5 (M = Cr, Mo) entities, while fragmentation occurs in reactions with N-heterocyclic carbenes [ 13 , 14 ]. Beside transition metal compounds, P 4 can be activated by main group electrophiles [ 2 , 15 ].…”
Section: Introductionmentioning
confidence: 99%