TY - JOUR
T1 - Synthesis and Characterization of Bulky 1,3-Diamidopropane Complexes of Group 2 Metals (Be−Sr)
AU - Nguyen, Dat T.
AU - Helling, Christoph
AU - Jones, Cameron
N1 - Funding Information:
We thank the Australian Research Council for funding. Moreover, this material is based upon work supported by the Air Force Office of Scientific Research under award number FA2386\u201021\u20101\u20104048. C.H. thanks the Alexander von Humboldt Foundation for a Feodor Lynen fellowship. Part of this research was undertaken on the MX1 beam line at the Australian Synchrotron, Victoria, Australia. Open Access publishing facilitated by Monash University, as part of the Wiley \u2010 Monash University agreement via the Council of Australian University Librarians.
Publisher Copyright:
© 2024 The Authors. Chemistry - An Asian Journal published by Wiley-VCH GmbH.
PY - 2024/8/1
Y1 - 2024/8/1
N2 - Reaction of lithium 1,3-diamidopropane Li2(TripNCN) (TripNCN=[{(Trip)NCH2}2CH2]2−, Trip=2,4,6-triisopropylphenyl) with BeBr2(OEt2)2 gave the diamido beryllium complex, [(TripNCN)Be(OEt2)]. Deprotonation reactions between the bulkier 1,3-diaminopropane (TCHPNCN)H2 (TCHPNCN=[{(TCHP)NCH2}2CH2]2−, TCHP=2,4,6-tricyclohexylphenyl) and magnesium alkyls afforded the adduct complexes [(TCHPNCN)Mg(OEt2)] and [(TCHPNCN)Mg(THF)2], depending on the reaction conditions employed. Treating [(TCHPNCN)Mg(THF)2] with the N-heterocyclic carbene :C{(MeNCMe)2} (TMC) gave [(TCHPNCN)Mg(TMC)2] via substitution of the THF ligands. Reactions of (ArNCN)H2 (Ar=Trip or TCHP) with Mg{CH2(SiMe3)}2, in the absence of Lewis bases, yielded the N-bridged dimers [{(ArNCN)Mg}2]. Salt metathesis reactions between alkali metal salts M2(TCHPNCN) (M=Li or K) and CaI2 or SrI2 led to the THF adduct compounds [(TCHPNCN)Ca(THF)3] and [(TCHPNCN)Sr(THF)4], the differing number of THF ligands in which is a result of the different sizes of the metals involved. The described complexes hold potential as precursors to kinetically protected, low oxidation state group 2 metal species.
AB - Reaction of lithium 1,3-diamidopropane Li2(TripNCN) (TripNCN=[{(Trip)NCH2}2CH2]2−, Trip=2,4,6-triisopropylphenyl) with BeBr2(OEt2)2 gave the diamido beryllium complex, [(TripNCN)Be(OEt2)]. Deprotonation reactions between the bulkier 1,3-diaminopropane (TCHPNCN)H2 (TCHPNCN=[{(TCHP)NCH2}2CH2]2−, TCHP=2,4,6-tricyclohexylphenyl) and magnesium alkyls afforded the adduct complexes [(TCHPNCN)Mg(OEt2)] and [(TCHPNCN)Mg(THF)2], depending on the reaction conditions employed. Treating [(TCHPNCN)Mg(THF)2] with the N-heterocyclic carbene :C{(MeNCMe)2} (TMC) gave [(TCHPNCN)Mg(TMC)2] via substitution of the THF ligands. Reactions of (ArNCN)H2 (Ar=Trip or TCHP) with Mg{CH2(SiMe3)}2, in the absence of Lewis bases, yielded the N-bridged dimers [{(ArNCN)Mg}2]. Salt metathesis reactions between alkali metal salts M2(TCHPNCN) (M=Li or K) and CaI2 or SrI2 led to the THF adduct compounds [(TCHPNCN)Ca(THF)3] and [(TCHPNCN)Sr(THF)4], the differing number of THF ligands in which is a result of the different sizes of the metals involved. The described complexes hold potential as precursors to kinetically protected, low oxidation state group 2 metal species.
KW - beryllium
KW - bulky ligand
KW - calcium
KW - diamide
KW - magnesium
KW - strontium
UR - https://www.scopus.com/pages/publications/85196855460
U2 - 10.1002/asia.202400498
DO - 10.1002/asia.202400498
M3 - Article
AN - SCOPUS:85196855460
SN - 1861-4728
VL - 19
JO - Chemistry - An Asian Journal
JF - Chemistry - An Asian Journal
IS - 15
M1 - e202400498
ER -