Bis(2,6-diisopropylphenyl)carbodiimide

Versatile reactivities of rare-earth metal dialkyl complexes supported by a neutral pyrrolyl-functionalized beta-diketiminato ligand.[Pubmed:29459931]

Dalton Trans. 2018 Mar 12;47(11):3947-3957.

Herein, rare-earth metal dialkyl complexes supported by a neutral pyrrolyl-functionalized beta-diketiminato ligand with the formula LRE(CH2SiMe3)2(thf) (RE = Y (1a), Dy (1b), Er (1c), Yb (1d); L = MeC(NDipp)CHC(Me)NCH2CH2NC4H2-2,5-Me2, Dipp = 2,6-(i)Pr2C6H3) were synthesized via the reactions of the beta-diketimine HL with the rare-earth metal trialkyl complexes RE(CH2SiMe3)3(thf)2 in high yields. The reactivities of 1 with pyridine derivatives, unsaturated substrates, and elemental sulfur were investigated, and some interesting chemical transformations were observed. Ligand exchange and activation of sp(2) and sp(3) C-H bonds occurred during the reactions with pyridine derivatives to afford different types of mononuclear rare-earth metal pyridyl complexes, namely, LEr(CH2SiMe3)2(eta(1)-NC5H4) (2c), LRE(eta(3)-CH2-2-NC5H2-4,6-Me2)2 (RE = Y (3a), Er (3c)), and LRE(CH2SiMe3)(eta(2)-(C,N)-2-(2-C6H4NC5H4)) (RE = Er (4c), Yb = (4d)). Similarly, activation of the sp C-H bond occurred during the reaction of phenylacetylene with 1c to produce the dinuclear erbium alkynyl complex [LEr(CH2SiMe3)(mu-C[triple bond, length as m-dash]CPh)]2 (5c). The mixed amidinate-beta-diketiminato ytterbium complex LYb[(Dipp)NC(CH2SiMe3)N(Dipp)](CH2SiMe3) (6d) was obtained by the insertion of Bis(2,6-diisopropylphenyl)carbodiimide into a Yb-alkyl bond, as well as via the direct alkane elimination of a CH2SiMe3 moiety with bis(2,6-diisopropylphenyl)formamidine to afford the erbium complex LEr(DippNCHNDipp)(CH2SiMe3) (7c). A rare sp(2) C-H bond oxidation of the beta-diketiminato backbone with elemental sulfur insertion was detected to provide the unprecedented dinuclear rare-earth metal thiolate complexes (LRE)2(mu-SCH2SiMe3)2(mu-SCC(Me)(NDipp)C(Me)NCH2CH2NC4H2Me2-2,5) (RE = Y (8a), Er (8c)) in the reactions of S8 with 1a and 1c, respectively. The molecular structures of the complexes 1-8 were determined by single-crystal X-ray diffraction analyses.

Synthesis, structure and reactivity of a donor-stabilised silylene with a bulky bidentate benzamidinato ligand.[Pubmed:26228381]

Dalton Trans. 2015 Sep 7;44(33):14959-74.

The novel donor-stabilised silylene was prepared in a four-step synthesis, starting from Bis(2,6-diisopropylphenyl)carbodiimide (Dipp-N[double bond, length as m-dash]C[double bond, length as m-dash]N-Dipp), and its reactivity was studied in a series of oxidative addition reactions and a nucleophilic substitution reaction. The three-coordinate silicon(ii) complex contains the bulky bidentate amidinato ligand Dipp-NC(Ph)N-Dipp(-) and a dimethylamido ligand. Treatment of with N2O afforded the dinuclear five-coordinate silicon(iv) complex (SiO2N3 skeletons), and the reaction with S8 yielded the dinuclear four-coordinate silicon(iv) complex (SiS2N2 skeletons). Treatment of with Se and Te afforded the respective four-coordinate silicon(iv) complexes (SiSeN3 skeleton) and (SiTeN3 skeleton), which contain an Si[double bond, length as m-dash]Se and Si[double bond, length as m-dash]Te double bond, respectively. The reaction of with the silyl azide Me3SiN3 yielded the four-coordinate silicon(iv) complex (SiN4 skeleton) with an Si[double bond, length as m-dash]N double bond, whereas the reaction with the alkyl azide PhSCH2N3 gave the four-coordinate silicon(iv) complex (SiSN3 skeleton), the first silicon(iv) complex with an unsubstituted methyleneamido ligand. The reaction of with [Fe(CO)5] afforded the four-coordinate silicon(ii) complex (SiFeN3 skeleton) with an Si-Fe bond. Compounds (and the precursors and (five-coordinate silicon(iv) complexes with an SiCl3N2 and SiCl2N3 skeleton, respectively) in the synthesis of ) were characterised by elemental analyses, crystal structure analyses and multinuclear NMR spectroscopic studies in the solid state and in solution.

The 2-phosphaethynolate anion: a convenient synthesis and [2+2] cycloaddition chemistry.[Pubmed:23913436]

Angew Chem Int Ed Engl. 2013 Sep 16;52(38):10064-7.

Hip to be square: Direct carbonylation of solutions of the heptaphosphide trianion (P7(3-)) afforded the phosphaethynolate anion in moderate yields. This species undergoes [2+2] cycloaddition reactions with diphenylketene and Bis(2,6-diisopropylphenyl)carbodiimide to yield the anionic four-membered heterocycles P[C(O)]2C(C6H5)2(-) and PC(O)(CNDipp)NDipp(-) .

Studies on the reactivity of group 15 Zintl ions with carbodiimides: synthesis and characterization of a heptaphosphaguanidine dianion.[Pubmed:21681304]

Chem Commun (Camb). 2012 Feb 1;48(10):1470-2.

Reaction of the hydrogenheptaphosphide dianion, [HP(7)](2-), with one equivalent of Bis(2,6-diisopropylphenyl)carbodiimide yielded the exo-functionalized cluster [P(7)C(NDipp)(NHDipp)](2-) (Dipp = 2,6-diisopropylphenyl). This species was characterized by single crystal X-ray diffraction, multielement NMR spectroscopy and electrospray mass-spectrometry. DFT calculations on the dianion were also conducted.