Research output: Contribution to journal › Article › peer-review
Different reductive reactivities of SmCpx 2(THF)n (Cpx = C5Me5 and C5H3 tBu2) samarocenes toward P2Ph4 : THF ring-opening and ligand-exchange pathways. / Pushkarevsky, Nikolay A.; Ilyin, Igor Yu; Petrov, Pavel A. et al.
In: Organometallics, Vol. 36, No. 7, 10.04.2017, p. 1287-1295.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Different reductive reactivities of SmCpx 2(THF)n (Cpx = C5Me5 and C5H3 tBu2) samarocenes toward P2Ph4
T2 - THF ring-opening and ligand-exchange pathways
AU - Pushkarevsky, Nikolay A.
AU - Ilyin, Igor Yu
AU - Petrov, Pavel A.
AU - Samsonenko, Denis G.
AU - Ryzhikov, Maxim R.
AU - Roesky, Peter W.
AU - Konchenko, Sergey N.
PY - 2017/4/10
Y1 - 2017/4/10
N2 - The reduction of tetraphenyldiphosphine with two differently substituted samarocenes(II) proceeds via different pathways. With [SmCp∗ 2(THF)2] (Cp∗ = η5- C5Me5), the reaction had been known to result in the THF ring-opening product, [SmCp∗ 2(O(CH2)4PPh2)], 3, owing to the instability of phosphido complex [SmCp∗ 2(PPh2)] in the presence of THF. Complex 3 crystallizes from apolar solvents as dimeric or polymeric polymorph with butoxo-phosphine bridging ligands in both cases. In contrast, the phosphide [SmCp″2(PPh2)] (Cp″ = η5-1,3-C5H3 tBu2), 5, is not prone to ring-opening owing to insufficient space in the Sm coordination sphere for a THF ligand. Product 5 is inevitably accompanied by homoleptic complex [SmCp″3] 6 and dinuclear mixed-valent complex [SmIIICp″2(μ-PPh2)2SmIICp″] 7 as the further products of redox transformations and ligand exchange. The formation of 5-7 is rationalized by a sequence of initial coordination of one or two {SmIICp″2} fragments by P atoms and reductive elimination of PPh2· or Cp″·E radicals. Further reaction with another equivalent of [SmCp″2] results in the trapping the radicals and formation of all three products.
AB - The reduction of tetraphenyldiphosphine with two differently substituted samarocenes(II) proceeds via different pathways. With [SmCp∗ 2(THF)2] (Cp∗ = η5- C5Me5), the reaction had been known to result in the THF ring-opening product, [SmCp∗ 2(O(CH2)4PPh2)], 3, owing to the instability of phosphido complex [SmCp∗ 2(PPh2)] in the presence of THF. Complex 3 crystallizes from apolar solvents as dimeric or polymeric polymorph with butoxo-phosphine bridging ligands in both cases. In contrast, the phosphide [SmCp″2(PPh2)] (Cp″ = η5-1,3-C5H3 tBu2), 5, is not prone to ring-opening owing to insufficient space in the Sm coordination sphere for a THF ligand. Product 5 is inevitably accompanied by homoleptic complex [SmCp″3] 6 and dinuclear mixed-valent complex [SmIIICp″2(μ-PPh2)2SmIICp″] 7 as the further products of redox transformations and ligand exchange. The formation of 5-7 is rationalized by a sequence of initial coordination of one or two {SmIICp″2} fragments by P atoms and reductive elimination of PPh2· or Cp″·E radicals. Further reaction with another equivalent of [SmCp″2] results in the trapping the radicals and formation of all three products.
KW - RAY CRYSTAL-STRUCTURE
KW - DIVALENT LANTHANIDE CHEMISTRY
KW - RARE-EARTH-ELEMENTS
KW - ELECTRON-DENSITY
KW - STRUCTURAL-CHARACTERIZATION
KW - MOLECULAR-COMPLEXES
KW - SUPERBULKY LIGANDS
KW - OXIDATION-STATE
KW - BOND FORMATION
KW - BASIS-SETS
UR - http://www.scopus.com/inward/record.url?scp=85019645882&partnerID=8YFLogxK
U2 - 10.1021/acs.organomet.7b00014
DO - 10.1021/acs.organomet.7b00014
M3 - Article
AN - SCOPUS:85019645882
VL - 36
SP - 1287
EP - 1295
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 7
ER -
ID: 10191226