Extending the Family of N‐Heterocyclic Heavy Carbene Analogues: Synthesis and Crystal and Molecular Structures of MeN[CH₂C(O)N(R)]₂Sn (R = Me₂NCH₂CH₂, PhCH₂, Me₃CCH₂)

Abstract

We report herein the synthesis of the N-methyl-NЈNЈЈ-diorganoiminodiacetic acid diamides MeN[CH 2 C(O)N(R)H] 2 [3: R = Me 2 N(CH 2 ) 2 ; 4: R = PhCH 2 ; 5: R = Me 3 CCH 2 ] and the novel tin(II) derivatives MeN[CH 2 C(O)N(R)] 2 Sn [6: R = Me 2 N(CH 2 ) 2 ; 7: R = PhCH 2 ; 8: R = Me 3 CCH 2 ]. The compounds were characterized by elemental analyses, 1 H NMR spectroscopy (3-5), solid-state 13 C and 119 Sn NMR spectroscopy (8), and single-crystal X-ray diffraction analysis (5,[a] 5836 8). Compound 8 shows intramolecular NǞSn and intermolecular OǞSn interactions with distances of 2.370(2) and 2.406(2) Å, respectively, the latter indicating that 8 is a coordination polymer. DFT calculations revealed covalent Sn-NC(O) and coordinative NǞSn and C=OǞSn bonds. The wB97Xd functional, which takes into account dispersive interactions, was employed for a correct theoretical description of, in particular, the latter bond. molecular coordination of a built-in donor function that fills the vacant p z orbital at the tin atom with electron density. [6][7][8][9] Sometimes this is achieved in combination with steric protection. In the case of tin(II) amides, this has been demonstrated for the intramolecularly coordinated compounds A, [10] B, [11] C, [12a] and D [12b] (Scheme 1). Scheme 1.

Synthesis of ONO‐Ligated Tetrylenes Based on 2,6‐bis(2‐Hydroxyphenyl)pyridines: Influence of Ligand Sterics on the Structure of the Products

“…For this compound, only its composition was studied by elemental analysis. The formation of such agglomerates is observed in the case of insufficient steric stabilization of tetrylenes [16–17] …”

“…The formation of such agglomerates is observed in the case of insufficient steric stabilization of tetrylenes. [16][17] The molecular structure of 6 (in C 6 D 6 ) was investigated by DOSY NMR spectroscopy to determine the association of the complex (see Supporting Information for details, Figure S21). [18] Excess free ligand 4 c is also included on the plot.…”

N‐Alkoxy Carboxamide Stabilized Tin(II) and Germanium(II) Complexes for Thin‐Film Applications

“…The crystal structure of 10 is displayed in Figure and is isostructural to that of 5 . The central metal atoms in both 5 and 10 showed distorted pseudo‐trigonal‐bipyramidal geometries, in which the methoxy oxygen atoms occupy the top of the pyramid and the amide oxygen atoms and a lone pair of electrons are placed at the equatorial positions. In 5 , the Ge(1)–O(1) and Ge(1)–O(3) bond lengths (Table ) of 2.226(19) and 2.2509(18) Å, respectively, are understandably much longer than previously reported Ge–alkoxide bonds because of their purely coordinative characteristics.…”