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. 2024 Feb 12;63(6):3118-3128.
doi: 10.1021/acs.inorgchem.3c04135. Epub 2024 Jan 30.

Amidinatotetrylenes Donor Functionalized on Both N Atoms: Structures and Coordination Chemistry

Christian Alonso  1 , Javier A Cabeza  1 , Pablo García-Álvarez  1 , Rubén García-Soriano  1 , Enrique Pérez-Carreño  2
Affiliations

Amidinatotetrylenes Donor Functionalized on Both N Atoms: Structures and Coordination Chemistry

Christian Alonso et al. Inorg Chem. .

Abstract

E(hmds)(bqfam) (E = Ge (1a), Sn (1b); hmds = N(SiMe3)2, bqfam = N,N'-bis(quinol-8-yl)formamidinate), which are amidinatotetrylenes equipped with quinol-8-yl fragments on the amidinate N atoms, have been synthesized from the formamidine Hbqfam and Ge(hmds)2 or SnCl(hmds). Both 1a and 1b are fluxional in solution at room temperature, as the E atom oscillates from being attached to the two amidinate N atoms to being chelated by an amidinate N atom and its closest quinolyl N atom (both situations are similarly stable according to density functional theory calculations). The hmds group of 1a and 1b is still reactive and the deprotonation of another equivalent of Hbqfam can be achieved, allowing the formation of the homoleptic derivatives E(bqfam)2 (E = Ge, Sn). The reactions of 1a and 1b with [AuCl(tht)] (tht = tetrahydrothiophene), [PdCl2(MeCN)2], [PtCl2(cod)] (cod = cycloocta-1,5-diene), [Ru3(CO)12] and [Co2(CO)8] have been investigated. The gold(I) complexes [AuCl{κE-E(hmds)(bqfam)}] (E = Ge, Sn) have a monodentate κE-tetrylene ligand and display fluxional behavior in solution the same as that of 1a and 1b. However, the palladium(II) and platinum(II) complexes [MCl{κ3E,N,N'-ECl(hmds)(bqfam)}] (M = Pd, Pt; E = Ge, Sn) contain a κ3E,N,N'-chloridotetryl ligand that arises from the insertion of the tetrylene E atom into an M-Cl bond and the coordination of an amidinate N atom and its closest quinolyl N atom to the metal center. Finally, the binuclear ruthenium(0) and cobalt(0) complexes [Ru2{μE-κ3E,N,N'-E(hmds)(bqfam)}(CO)6] and [Co2{μE-κ3E,N,N'-E(hmds)(bqfam)}(μ-CO)(CO)4] (E = Ge, Sn) have a related κ3E,N,N'-tetrylene ligand that bridges two metal atoms through the E atom. For the κ3E,N,N'-metal complexes, the quinolyl fragment not attached to the metal is pendant in all the germanium compounds but, for the tin derivatives, is attached to (in the Pd and Pt complexes) or may interact with (in the Ru2 and Co2 complexes) the tin atom.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Types of currently known metal-free potentially polydentate ATs.
Figure 2
Figure 2
Currently known, including this work, potentially tridentate ligands featuring an AT fragment in the central position.
Scheme 1
Scheme 1. Reactions Leading to Compounds 1a, 1b, 2a, and 2b
Figure 3
Figure 3
SCXRD molecular structure of 1b [only one of the two positions in which one of the SiMe3 groups (Si1) is disordered is shown; 50% displacement ellipsoids; H atoms omitted for clarity]. Selected interatomic distances (Å) and angles (°): Sn1···N3 2.869(1), Sn1–N1 2.381(1), Sn1–N2 2.174(1), Sn1–N5 2.122(1) N2–C10 1.352(2), N3–C10 1.297(2); N3–C10–N2 116.4(1), N5–Sn1–N2 101.09(5), N5–Sn1–N1 93.05(5), N2–Sn1–N1 70.19(5).
Figure 4
Figure 4
Dynamic behavior found for 1a and 1b in solution (top) and DFT-calculated (wB97xd/SDD(Ge,Sn)/cc-pVDZ) energy profile for the κN-amidinate (1r5E) to κ2N,N′-amidinate (1r4E) interconversion for E= Ge, Sn. For clarity, the optimized structures of the transition states (TS) are not shown here but are shown in Figure S17. Gibbs energies (CPCM-toluene) are given in kcal mol–1. Interatomic distances are given in Å.
Scheme 2
Scheme 2. Syntheses of Compounds 3a and 3b and Their Dynamic Behavior in Solution
Figure 5
Figure 5
SCXRD molecular structure of 3a (30% displacement ellipsoids; H atoms omitted for clarity). Selected interatomic distances (Å) and angles (deg): Au1–Ge1 2.3280(8), Au1–Cl1 2.306(2), Ge1···N3 2.963(5), Ge1–N1 2.025(6), Ge1–N2 1.905(5), Ge1–N5 1.841(5); N2–C10 1.364(9), N3–C10 1.283(8); Cl1–Au1–Ge1 177.81(5), N3–C10–N2 118.0(6), N5–Ge1–N2 113.7(2), N5–Ge1–N1 102.9(2), N2–Ge1–N1 81.6(2), N5–Ge1–Au1 121.2(2), N2–Ge1–Au1 117.3(2), N1–Ge1–Au1 111.4(2).
Scheme 3
Scheme 3. Syntheses of Compounds 4a, 4b, 5a, and 5b
Figure 6
Figure 6
SCXRD molecular structures of 4a (top) and 4b (bottom) (30% displacement ellipsoids, H atoms omitted for clarity). Selected interatomic distances (Å) and angles (deg): 4a: Pd1–Ge1 2.2839(5), Pd1–Cl2 2.298(1), Pd1–N3 2.004(3), Pd1–N4 2.106(3), Ge1–N2 1.971(3), Ge1–N5 1.820(4), Ge1–Cl1 2.211(1), N2–C10 1.339(5), N3–C10 1.320(5); N3–Pd1–N4 80.8(1), N3–Pd1–Ge1 84.78(9), N4–Pd1–Ge1 165.5(1), N3–Pd1–Cl2 176.1(1), N4–Pd1–Cl2 101.9(1), Ge1–Pd1–Cl2 92.56(3), N3–C10–N2 121.6(4), N5–Ge1–N2 109.3(1), N5–Ge1–Cl1 106.1(1), N2–Ge1–Cl1 98.5(1), N5 Ge1 Pd1 129.9(1), N2–Ge1–Pd1 95.8(1), Cl1–Ge1–Pd1 112.39(3). 4b: Pd1–Sn1 2.4936(3), Pd1–Cl2 2.2967(9), Pd1–N3 2.016(3), Pd1–N4 2.124(3), Sn1–N1 2.314(3), Sn1–N2 2.248(3), Sn1–N5 2.107(3), Sn1–Cl1 2.431(1), N2–C10 1.336(5), N3–C10 1.305(5); N3–Pd1–N4 80.8(1), N3–Pd1–Sn1 89.64(9), N4–Pd1–Sn1 170.39(9), N3–Pd–Cl2 179.1(1), N4–Pd1–Cl2 98.82(9), Sn1–Pd1–Cl2 92.72(3), N3–C10–N2 122.4(3), N5–Sn1–N2 122.4(1), N5–Sn1–N1 85.6(1), N2–Sn1–N1 69.9(1), N5–Sn1–Cl1 116.40(9), N2–Sn1–Cl1 108.55(9), N1–Sn1–Cl1 81.76(9), N5 Sn1 Pd1 112.99(9), N2–Sn1–Pd1 85.44(8), N1–Sn1–Pd1 155.34(8), Cl1–Sn1–Pd1 105.97(3).
Scheme 4
Scheme 4. Syntheses of Compounds 6a, 6b, 7a, and 7b
Figure 7
Figure 7
SCXRD molecular structure of 6a (top; 30% displacement ellipsoids) and the DFT-optimized structure of 6b (bottom). H atoms been omitted for clarity. Selected interatomic distances (Å) and angles (deg): 6a: Ru1–Ge1 2.3898(3), Ru1–Ru2 2.9628(3), Ru1–N3 2.109(2), Ru1–N4 2.176(2), Ge1–N2 1.992(2), Ge1···N1 3.600(2), Ge1–N5 1.862(2), Ge1–Ru2 2.5063(3), N2–C10 1.330(3), N3–C10 1.320(3); N3–C10–N2 121.3(2), N5–Ge1–N2 102.6(1) N5–Ge1–Ru2 132.02(7), N2–Ge1–Ru2 111.38(6), N5–Ge1–Ru1 135.15(7), N2–Ge1–Ru1 95.91(6), Ru1–Ge1–Ru2 74.43(1) 6b: Ru1–Sn1 2.560, Ru1–Ru2 3.130, Ru1–N3 2.152, Ru1–N4 2.202, Sn1–N2 2.209, Sn1···N1 3.044, Sn1–N5 2.024, Sn1–Ru2 2.662, N2–C10 1.324, N3–C10 1.320; N3–C10–N2 123.11, N5–Sn1–N2 100.65, N5–Sn1–Ru2 140.28, N2–Sn1–Ru2 109.14, N5Sn1Ru1 133.47, N2–Sn1–Ru1 89.34, Ru1–Sn1–Ru2 73.63.
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