Reaction of Sulfur with Ga−C Bonds:  Synthesis and Characterization of [PyRGaS]₃ Formed from Ga(S₂R)₃ (R = Et, Me)

Abstract

The reactions of Ga(CH(2)CH(3))(3) with variable amounts of elemental sulfur, S(8), in toluene or benzene at different temperatures result in the insertion of sulfur into the Ga-C bonds to form the compounds Ga[(S-S)CH(2)CH(3)](3) (I) and Ga[(S-S-S)CH(2)CH(3)](3) (II). Compound I was isolated from the reaction at low temperature while at room temperature; compound II was the major product. Compound II exhibited the maximum extent of sulfur insertion even when the reactions were carried out with more than 9.0 equiv of sulfur. The reactions of Ga(CH(3))(3) with various amounts of sulfur in toluene or benzene only result in the formation of compound III, Ga[(S-S)CH(3)](3). In pyridine at -30 degrees C, deinsertion of the sulfur atoms from Ga-S-S-C bonds was observed for the first time from compounds I and III resulting in formation of the six-membered Ga-S ring compounds IV, [PyEtGaS](3), and V, [PyMeGaS](3), respectively. Compounds IV and V were characterized by (1)H NMR, (13)C NMR, elemental analyses, thermogravimetric analysis, and single-crystal X-ray diffraction. Compound IV crystallized in the monoclinic space group P2(1)/n, with a = 9.288(2) Å, b = 14.966(2) Å, c = 19.588(3) Å, beta = 90.690(10) degrees, and Z = 4. Compound V crystallized in the monoclinic space group P2(1)/c, with a = 10.385(1) Å, b = 15.300(2) Å, c = 15.949(2) Å, beta = 107.01(1) degrees, Z = 4, unit cell volume = 2423.5(5) Å(3), R = 0.030, and R(w) = 0.026. The sulfur insertion reaction pathway was investigated by time-dependent and variable-temperature (1)H NMR spectroscopy.

Insertion, Isomerization, and Cascade Reactivity of the Tethered Silylalkyl Uranium Metallocene (η5-C5Me4SiMe2CH2-κC)2U

“…The formation of (η 5 :η 2 -C 5 Me 4 SiMe 2 CH 2 S 2 ) 2 U ( 2 ) (eq ) represents the first example of insertion of elemental sulfur into a U−C bond, and it provides the first f element complex with an alkyl disulfide ligand. Alkyl disulfide ligands from sulfur insertion are known with W and Ga, but in general they are rare. , In the past, organoactinide complexes of alkyl sulfides have been made primarily from RSH, − RSM (M = alkali metal), − CS 2 insertion, and RSSR substrates. ,,, To our knowledge, there is only a single example of the use of S 8 as a reagent in organoactinide chemistry in the formation of [U(N t Bu) 2 (I)( t Bu 2 bpy)] 2 (μ,η 2 :η 2 -S 4 ) from [U(N t Bu) 2 (I)( t Bu 2 bpy)] 2 . Insertion of sulfur into lanthanide−alkyl bonds using S 8 is known with organolanthanides such as [(C 5 H 4 R) 2 LnR′] x , , where R = H, SiMe 2 t Bu and R′ = Me, n -Bu.…”

“…The formation of (η 5 :η 2 -C 5 Me 4 SiMe 2 CH 2 S 2 ) 2 U (2) (eq 3) represents the first example of insertion of elemental sulfur into a U-C bond, and it provides the first f element complex with an alkyl disulfide ligand. Alkyl disulfide ligands from sulfur insertion are known with W 54 and Ga, 55 but in general they are rare. 56,57 In the past, organoactinide complexes of alkyl sulfides have been made primarily from RSH, [58][59][60] RSM (M = alkali metal), [61][62][63] CS 2 insertion, 43 and RSSR substrates.…”

Preparation and structure of soluble complexes of the ternary compounds GaSBr and GaSeBr

“…The structure of 4 was refined as a merohedral twin. The refined BASF parameter for the merohedral twinning is 0.3373 (16). Further informations on crystal data, data collection and structure refinement are summarized in Tables 1 and 2.…”

Synthesis and characterization of gallium thiocarboxylates as novel single-source precursors to gallium sulfide thin films by aerosol-assisted CVD

“…The analytical and spectroscopic data for 1 were all consistent with the solid-state X-ray diffraction results and other structurally characterized Ga compounds. [18][19][20] In contrast, the reaction of GaEt3 with 3.0 equiv. of thioacetic acid in toluene in the presence of dmpy gave rise to the formation of Ga(SCOMe)3(dmpy).…”