Synthesis and Characterization of Ruthenium Germyl Complexes with Various Substituents

doi:10.6023/cjoc202308002

Abstract

Reactions of dichlorogermyl ruthenium complexes (PPh₃)(X)RuGeCl₂ArTrip (X=H, 1; Cl, 2; ArTrip=C₆H₃-2- (η⁶-Trip)-6-Trip, Trip=2,4,6-ⁱPr₃-C₆H₃) with various reagents, including Grignard reagent, LiHBEt₃ and Na/naphthalene were investigated, realizing the substituent modulation on Ge and Ru atoms. 1 reacted with EtMgBr forming (PPh₃)HRu- GeBr₂ArTrip (3) and (PPh₃)HRuGeEt₂ArTrip (4) depending on the reaction temperature. The reaction of 1 with LiHBEt₃ also resulted in the formation of 4, where LiHBEt₃ acted as ethyl transfer reagent instead of hydrogenation reagent. Additionally, 1 reacted with HBF₄ afforded ionic product [(PPh₃)H₂RuGeCl₂ArTrip][BF₄] (5). On the other hand, reduction of 2 with Na/naphthalene produced dihydroxyl complex (PPh₃)HRuGe(OH)₂ArTrip (6), while the reaction with I₂ underwent monoiodination on Ru with the formation of (PPh₃)IRuGeCl₂ArTrip (7). All compounds were fully characterized by heteronuclear NMR spectroscopy and single-crystal X-ray diffraction.

Key words: ruthenium, germylene, substitution, structure

Cite this article

Yan Tian, Rui Dong, Peng Nie, Bo Xu. Synthesis and Characterization of Ruthenium Germyl Complexes with Various Substituents[J]. Chinese Journal of Organic Chemistry, 2024, 44(1): 173-179.

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Fig. & Tab. 7

Scheme 1. Selected examples of Ru-germylene and Ru-germyl complexes

Scheme 2. Synthesis of 3~5

Figure 1. Molecular structure of 3 with thermal ellipsoids at 30% probability level All hydrogen atoms are omitted for clarity.

Figure 2. Molecular structures of 4 and 5 with thermal ellipsoids at 30% probability level All hydrogen atoms are omitted for clarity.

Compd.	1^[8f]	2^[8f]	3	4	6	7
Ru—Ge	2.391(8)	2.433(5)	2.393(0)	2.448(8)	2.396(6)	2.401(1)
Ru—P	2.299(2)	2.359(5)	2.308(1)	2.270(4)	2.281(2)	2.340(3)
Ge—C	1.997(3)	1.984(3)	2.005(6)	2.043(4)	1.994(9)	1.992(1)
Ge—Ru—P	95.66(3)	94.04(3)	97.32(5)	94.73(4)	92.82(6)	95.96(8)
C—Ge—Ru	105.96(1)	106.64(8)	106.74(2)	100.85(1)	103.8(2)	104.9(3)

Table 1. Selected bond lengths (?) and angles (o) of 1~4, 6 and 7

Scheme 3. Synthesis of 6 and 7

Figure 3. Molecular structures of 6 and 7 with thermal ellipsoids at 30% probability level All hydrogen atoms and solvent molecule are omitted for clarity.

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