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. 2025 Mar 19;44(7):802-806.
doi: 10.1021/acs.organomet.5c00038. eCollection 2025 Apr 14.

Amidinate- and Dithiolene-Based Silicon Complexes

Yuzhong Wang  1 , John C Johnson  1 , Kayla G Palmer  1 , Pingrong Wei  1 , Earle R Adams  1 , Mitchell E Lahm  1 , Henry F Schaefer 3rd  1 , Gregory H Robinson  1
Affiliations

Amidinate- and Dithiolene-Based Silicon Complexes

Yuzhong Wang et al. Organometallics. .

Abstract

Reactions of the amidinato-silylene chloride PhC( t BuN)2SiCl (1) with imidazole-based dithione dimer 2, lithium dithiolene radical 3, and dithiolate dimer 4 result in the synthesis of a series of silicon complexes 5-7, respectively, containing both amidinato and dithiolene ligands. 7 is the first structurally characterized silicon(II) dithiolene complex. The structural and bonding characteristics of 5-7 have been probed by both experimental and theoretical methods.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Lewis base–dithiolene complexes (Dipp = 2,6-diisopropylphenyl): (I) carbene-stabilized dithiolene zwitterion; (II) spirocyclic dithiolene-based N-heterocyclic silane.
Figure 2
Figure 2
Amidinato-silylene-based low-oxidation-state main group clusters A–F (L = PhC(tBuN)2; Dipp = 2,6-diisopropylphenyl).
Scheme 1
Scheme 1. (a) Synthesis of 5–7 (R = 2,6-Diisopropylphenyl); (b) Proposed Mechanism for the Formation of 7
Figure 3
Figure 3
Molecular structures of 5, 6, and 7. Thermal ellipsoids represent 30% probability. Hydrogen atoms have been omitted for clarity. Selected bond distances (Å) and angles (deg) for 5: C(2)–C(3) 1.333(6); C(2)–S(2) 1.722(5); Si(1)–S(2) 2.1717(18); Si(1)–S(3) 2.2498(18); Si(1)–N(3) 1.906(4); Si(1)–N(4) 1.805(4); Si(1)–Cl(1) 2.0921(19); Cl(1)–Si(1)–S(2) 130.90(8); N(3)–Si(1)–S(3) 176.23(15). Selected bond distances (Å) and angles (deg) for 6: C(2)–C(3) 1.339(8); C(2)–S(2) 1.739(6); Si(1)–S(2) 2.258(2); Si(1)–S(3) 2.200(2); Si(1)–S(5) 2.175(2); Si(1)–N(7) 1.823(5); Si(1)–N(8) 1.933(5); C(29)–C(30) 1.343(7); C(29)–S(5) 1.740(6); N(8)–Si(1)–S(2) 178.88(17); S(3)–Si(1)–S(5) 137.07(10). Selected bond distances (Å) and angles (deg) for 7: C(2)–C(3) 1.346(5); C(2)–S(2) 1.728(3); Si(1)–S(2) 2.4291(13); Si(1)–S(3) 2.1987(13); Si(1)–N(3) 1.952(3); Si(1)–N(4) 1.838(3); Si(1)–Si(2) 2.3966(14); Si(2)–N(5) 1.870(3); Si(2)–N(6) 1.875(3); S(2)–Si(1)–N(3) 169.20(10); Si(2)–Si(1)–S(3) 138.11(5).
Figure 4
Figure 4
Amidinato-based bis(silylene) 8.
Figure 5
Figure 5
(a) HOMO–2 of 7 (the isosurface value for the orbital plot = 0.04; hydrogen atoms have been omitted for clarity). (b) Shaded relief map with projection effect of the electron localization function of 7 in the Si(2)–Si(1)–N(3) plane.
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References

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