Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
7747459 | Coordination Chemistry Reviews | 2018 | 95 Pages |
Abstract
In organoactinide chemistry, a rare homoleptic uranium(III) tris(aryl) complex, (Terph)3U (Terphâ¯=â¯C6H3-2,6-(C6H4-4-tBu)2), has been reported, and the synthesis and reactivity of homoleptic uranium(IV) tetrabenzyl complexes have been studied. Also notable among non-cyclopentadienyl actinide complexes is the phosphorano-stabilized Th(IV) carbene complex Th(CHPPh3)[N(SiMe3)2]3. Moreover, the synthesis, characterization, and reactivity of new heteroleptic Th and U complexes supported by the macrocyclic TMTAA ligand (TMTAAâ¯=â¯tetramethyl-tetraazaannulene) have been reported. Interesting derivative chemistry has been developed around the bis(NHC)borate-supported thorium bis(phosphido) complex Th(BcMes)2[HP(Mes)]2 (BcMesâ¯=â¯[H2B(C3H2N2Mes)2]â, Mesâ¯=â¯2,4,6-trimethylphenyl). A Novel diuranium µ-phosphido complex have also been prepared and structurally characterized, and the formation of a uranium-coordinated η1âcyaphide (CPâ) ligand via activation and CO bond cleavage of the phosphaethynolate (OCPâ) anion has been reported. Thorough reactivity studies have been carried out for actinide metallocene complexes such as ThCpâ³3 (Cpâ³â¯=â¯[C5H3(SiMe3)2-1,3], [η5-1,3-(Me3C)2C5H3]2U(η4-C4Ph2), Cpâ²4U (Cpâ²â¯=â¯C5H4SiMe3), Cpâ2U[η4-C4(SiMe3)2], Cpâ2U(bipy), Cpâ2ThN(mesityl)(DMAP) (DMAPâ¯=â¯4-dimethylaminopyridine) and Cpâ2Th[CHPPh3]X (Xâ¯=â¯Br, I). The complexes Cpâ2Th(EHTipp)2 (Eâ¯=â¯P, As; Tippâ¯=â¯2,4,6-triisopropylphenyl) have been used to access Th-E multiple bonds as in the terminal phosphinidene complex [K(2,2,2-cryptand)][Cpâ2Thâ¯=â¯PTipp(PHTipp)]. The synthesis, structure, and reactivity of the sterically crowded Th3+ complex Cpâ3Th have also been investigated in detail. Remarkable achievements have been made in 2017 in the organometallic chemistry of neptunium and plutonium. Structurally characterized compounds included e.g. Cp3Np, Cp3Np(NCMe)2, K[NpCp4], and Cpâ²3Np. Yet another highlight in this field was the first identification of the formal +2 oxidation state of plutonium in the organometallic complex [K(2.2.2-cryptand)][PuIICpâ³3]. This complex was prepared by reduction of Cpâ³3Pu with KC8 in the presence of 2.2.2-crypt and structurally characterized by X-ray diffraction. In a second contribution, the first X-ray crystal structure determination of an organometallic plutonium(IV) complex, the tetrasubstituted plutonocene complex Pu(1,3-COTâ³)(1,4-COTâ³) [COTâ³â¯=â¯Î·8-bis(trimethylsilyl)cyclooctatetraenyl], has been reported. Interesting studies involving organoactinides complexes in homogeneous catalysis have addressed e.g. the dimerization of aldehydes.
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Physical Sciences and Engineering
Chemistry
Inorganic Chemistry
Authors
Frank T. Edelmann,