TY - JOUR
T1 - Lanthanoid Biphenolates as a Rich Source of Lanthanoid-Main Group Heterobimetallic Complexes
AU - Ali, Safaa H.
AU - Shephard, Angus C.G.
AU - Wang, Jun
AU - Guo, Zhifang
AU - Davies, Murray S.
AU - Deacon, Glen B.
AU - Junk, Peter C.
N1 - Funding Information:
Open access publishing facolitated by James Cook University, as part of Wiley – James Cook University agreement via the Council of Australian University Librararians. This research was supported by Australian Research Council (DP190100798), Part of the research were undertaken on the MX1 beamline at the Australian Synchrotron, part of ANSTO. Open access publishing facilitated by James Cook University, as part of the Wiley ‐ James Cook University agreement via the Council of Australian University Librarians.
Funding Information:
Open access publishing facolitated by James Cook University, as part of Wiley ? James Cook University agreement via the Council of Australian University Librararians. This research was supported by Australian Research Council (DP190100798), Part of the research were undertaken on the MX1 beamline at the Australian Synchrotron, part of ANSTO. Open access publishing facilitated by James Cook University, as part of the Wiley - James Cook University agreement via the Council of Australian University Librarians.
Publisher Copyright:
© 2022 The Authors. Chemistry - An Asian Journal published by Wiley-VCH GmbH.
PY - 2022/3/1
Y1 - 2022/3/1
N2 - Several new trivalent dinuclear rare earth 2,2’-methylenebis(6-tert-butyl-4-methylphenolate) (mbmp2−) complexes with the general form [Ln2(mbmp)3(thf)n] (Ln=Sm 1, Tb 2 (n=3), and Ho 3, Yb 4 (n=2), and a tetravalent cerium complex [Ce(mbmp)2(thf)2] (5) have been synthesised by RTP (redox transmetallation/protolysis) reactions from lanthanoid metals, Hg(C6F5)2 and the biphenol mbmpH2. These new complexes and some previously reported partially protonated rare earth biphenolate complexes [Ln(mbmp)(mbmpH)(thf)n] react with lithium, aluminium, potassium and zinc organometallic reagents to form lanthanoid-main group heterobimetallic species. When reaction mixtures containing the Ln biphenolate complexes were treated with n-butyllithium, both molecular ([Li(thf)2Ln(mbmp)2(thf)n] (Ln=La 6, Pr 7 (n=2) and Er 8, Yb 9, and Lu 10 (n=1)) and charge separated ([Li(thf)4][Ln(mbmp)2(thf)2] (Ln=Y 11, Sm 12, Dy 13, and Ho 14) complexes were isolated. Treatment with trimethylaluminium also led to isolation of molecular ([AlMe2Ln(mbmp)2(thf)2] (Ln=Pr 15, Sm 16, and Tb 17)) and ionic [La(mbmp)(thf)5][AlMe2(mbmp)] (18) complexes. One gadolinium-potassium ([K(thf)3Gd(mbmp)2(thf)2] (19)), and one ytterbium-zinc species ([ZnEtYb(mbmp)2(thf)] (20)) were isolated from treatment of reaction mixtures with potassium bis(trimethylsilyl)amide and diethylzinc respectively.
AB - Several new trivalent dinuclear rare earth 2,2’-methylenebis(6-tert-butyl-4-methylphenolate) (mbmp2−) complexes with the general form [Ln2(mbmp)3(thf)n] (Ln=Sm 1, Tb 2 (n=3), and Ho 3, Yb 4 (n=2), and a tetravalent cerium complex [Ce(mbmp)2(thf)2] (5) have been synthesised by RTP (redox transmetallation/protolysis) reactions from lanthanoid metals, Hg(C6F5)2 and the biphenol mbmpH2. These new complexes and some previously reported partially protonated rare earth biphenolate complexes [Ln(mbmp)(mbmpH)(thf)n] react with lithium, aluminium, potassium and zinc organometallic reagents to form lanthanoid-main group heterobimetallic species. When reaction mixtures containing the Ln biphenolate complexes were treated with n-butyllithium, both molecular ([Li(thf)2Ln(mbmp)2(thf)n] (Ln=La 6, Pr 7 (n=2) and Er 8, Yb 9, and Lu 10 (n=1)) and charge separated ([Li(thf)4][Ln(mbmp)2(thf)2] (Ln=Y 11, Sm 12, Dy 13, and Ho 14) complexes were isolated. Treatment with trimethylaluminium also led to isolation of molecular ([AlMe2Ln(mbmp)2(thf)2] (Ln=Pr 15, Sm 16, and Tb 17)) and ionic [La(mbmp)(thf)5][AlMe2(mbmp)] (18) complexes. One gadolinium-potassium ([K(thf)3Gd(mbmp)2(thf)2] (19)), and one ytterbium-zinc species ([ZnEtYb(mbmp)2(thf)] (20)) were isolated from treatment of reaction mixtures with potassium bis(trimethylsilyl)amide and diethylzinc respectively.
KW - biphenolate ligands
KW - coordination chemistry
KW - heterobimetallic complexes
KW - rare earth complexes
KW - redox transmetallation
UR - https://www.scopus.com/pages/publications/85123623246
U2 - 10.1002/asia.202101328
DO - 10.1002/asia.202101328
M3 - Article
C2 - 35034432
AN - SCOPUS:85123623246
SN - 1861-471X
VL - 17
JO - Chemistry - An Asian Journal
JF - Chemistry - An Asian Journal
IS - 5
M1 - e202101328
ER -