TY - JOUR
T1 - Direct Reaction – One Step Route to Synthesize Lanthanoid-iodide Formamidinates**
AU - Guo, Zhifang
AU - Halim, Md Abdul
AU - Blair, Victoria L.
AU - Deacon, Glen B.
AU - Junk, Peter C.
N1 - Funding Information:
PCJ, GBD and VLB gratefully acknowledge the ARC for funding (DP230100112). Parts of this research were undertaken on the MX1 beamline at the Australian Synchrotron, part of ANSTO.[26] 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:
PCJ, GBD and VLB gratefully acknowledge the ARC for funding (DP230100112). Parts of this 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. [26]
Publisher Copyright:
© 2023 The Authors. Chemistry - An Asian Journal published by Wiley-VCH GmbH.
PY - 2023/7/17
Y1 - 2023/7/17
N2 - This paper describes a novel and simple method – direct reaction of lanthanoid metals with equimolar amounts of iodine and a formamidine under ultrasonication as an effective, metal-based route to lanthanoid(III) diiodide formamidinates, namely I. N,N′-Bis(2,6-diisopropylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(DippForm)I2(thf)3] (Ln=La, 1, Ce, 2, Tb, 3, Ho, 4, Er, 5, Tm, 6); II. N,N′-Bis(2,6-diethylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(EtForm)I2(thf)3] (Ln=Ce, 7, Nd, 8, Gd, 9, Tb, 10, Dy, 11, Ho, 12, Er, 13, Lu, 14). III. N,N′-bis(2,6-dimethylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(XylForm)I2(thf)3] (Ln=Ce, 15, Nd, 16, Gd, 17, Tm, 18, Lu 19); IV. N,N′-bis(phenyl)formamidinatodiiodidolanthanoid complexes [Ln(PhForm)I2(thf)3] (Ln=Nd, 20, Gd, 21, Er, 22). Compound [Ce(XylForm)2I(thf)2] (23) was also synthesized by the same method except the ratio of I2 to XylFormH was 1 : 4. Divalent N,N′-bis(2,6-diisopropylphenyl)formamidinato-iodido-lanthanoid(II) complexes [Eu(DippForm)I(thf)4] ⋅ thf (24), [Yb(DippForm)I(thf)3] ⋅ 2DippFormH (25), [Sm(DippForm)I(thf)4] ⋅ thf (26) have also been synthesized by direct reactions of the free metals, iodine and DippFormH. Interestingly, [Sm(DippForm)I2(thf)3] (27) was obtained by the oxidation of [Sm(DippForm)I(thf)4] ⋅ thf (26) on exposure to air. N,N′-Bis(2,6-dimethylphenyl)formamidinatoiodidosamarium(II) [Sm(XylForm)I(thf)3]n (28) was also prepared by direct reaction of Sm, iodine and XylFormH (mole ratio of I2: XylFormH=1 : 2). All products have been identified by X-ray crystallography and all the trivalent complexes [Ln(Form)nI3-n] (n=1 or 2) are stable to rearrangement.
AB - This paper describes a novel and simple method – direct reaction of lanthanoid metals with equimolar amounts of iodine and a formamidine under ultrasonication as an effective, metal-based route to lanthanoid(III) diiodide formamidinates, namely I. N,N′-Bis(2,6-diisopropylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(DippForm)I2(thf)3] (Ln=La, 1, Ce, 2, Tb, 3, Ho, 4, Er, 5, Tm, 6); II. N,N′-Bis(2,6-diethylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(EtForm)I2(thf)3] (Ln=Ce, 7, Nd, 8, Gd, 9, Tb, 10, Dy, 11, Ho, 12, Er, 13, Lu, 14). III. N,N′-bis(2,6-dimethylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(XylForm)I2(thf)3] (Ln=Ce, 15, Nd, 16, Gd, 17, Tm, 18, Lu 19); IV. N,N′-bis(phenyl)formamidinatodiiodidolanthanoid complexes [Ln(PhForm)I2(thf)3] (Ln=Nd, 20, Gd, 21, Er, 22). Compound [Ce(XylForm)2I(thf)2] (23) was also synthesized by the same method except the ratio of I2 to XylFormH was 1 : 4. Divalent N,N′-bis(2,6-diisopropylphenyl)formamidinato-iodido-lanthanoid(II) complexes [Eu(DippForm)I(thf)4] ⋅ thf (24), [Yb(DippForm)I(thf)3] ⋅ 2DippFormH (25), [Sm(DippForm)I(thf)4] ⋅ thf (26) have also been synthesized by direct reactions of the free metals, iodine and DippFormH. Interestingly, [Sm(DippForm)I2(thf)3] (27) was obtained by the oxidation of [Sm(DippForm)I(thf)4] ⋅ thf (26) on exposure to air. N,N′-Bis(2,6-dimethylphenyl)formamidinatoiodidosamarium(II) [Sm(XylForm)I(thf)3]n (28) was also prepared by direct reaction of Sm, iodine and XylFormH (mole ratio of I2: XylFormH=1 : 2). All products have been identified by X-ray crystallography and all the trivalent complexes [Ln(Form)nI3-n] (n=1 or 2) are stable to rearrangement.
KW - heteroleptic compounds
KW - Lanthanoids
KW - Rare earths
KW - structures
KW - synthesis
UR - http://www.scopus.com/inward/record.url?scp=85160262302&partnerID=8YFLogxK
U2 - 10.1002/asia.202300333
DO - 10.1002/asia.202300333
M3 - Article
C2 - 37203372
AN - SCOPUS:85160262302
SN - 1861-4728
VL - 18
JO - Chemistry - An Asian Journal
JF - Chemistry - An Asian Journal
IS - 14
M1 - e202300333
ER -