Dicarbonyl-1κ2C-μ-chlorido-2:3κ2Cl:Cl-penta­chlorido-2κ2Cl,3κ3Cl-[1(η6)-toluene]digallium(III)ruthenium(I)(Ru—Ga)

Smith, D.; Harakas, G.N.

doi:10.1107/S2414314624006576

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 9| Part 7| July 2024| x240657

https://doi.org/10.1107/S2414314624006576

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Dicarbonyl-1κ²C-μ-chlorido-2:3κ²Cl:Cl-pentachlorido-2κ²Cl,3κ³Cl-[1(η⁶)-toluene]digallium(III)ruthenium(I)(Ru—Ga)

Danielle Smith ^a and George N. Harakas ^a ^*

^aPO Box 6949, Radford University, Radford, Virginia 24142, USA
^*Correspondence e-mail: gharakas@radford.edu

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 2 July 2024; accepted 3 July 2024; online 9 July 2024)

The title compound, [RuGa₂Cl₆(C₇H₈)(CO)₂] or [(CO)₂(GaCl₂)(η⁶-toluene)Ru]⁺[GaCl₄]⁻, was isolated from the reaction of Ga₂Cl₄ with diphenylsilanediol in toluene, followed by the addition of Ru₃(CO)₁₂. The compound contains a ruthenium–gallium metal–metal bond with a length of 2.4575 (2) Å.

Keywords: crystal structure; ruthenium; gallium; metal–organic.

CCDC reference: 2367755

Structure description

The reaction of Ga₂Cl₄ with Ru₃(CO)₁₂ in toluene was demonstrated to produce two ruthenium–gallium metal clusters (Harakas & Whittlesey, 1997 ). The title compound (Fig. 1) was isolated during an attempt to synthesize the ruthenium–gallium diphenylsiloxane analogue of the previously reported iron–gallium dimethylsiloxane cluster (Demmin et al., 2024 ).

Figure 1
The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

The title compound can be described as [(CO)₂(GaCl₂)(η⁶-toluene) Ru]⁺ [GaCl₄]⁻. A single positive charge on the ruthenium complex provides a total of 18 electrons for the metal center with [GaCl₄]⁻ for charge balance. This bonding model is supported by the Ga1—Cl3 bond length of 2.4619 (5) Å, which is significantly longer than the other Ga—Cl bond lengths (Table 1) observed in the title compound. In contrast, [{CpFe(CO)₂}Ga(Cl*GaCl₃)(μ-Cl)]₂ is described as a Lewis acid–base complex i.e. [{CpFe(CO)₂}GaCl₂]₂·2GaCl₃ (Borovik et al., 1999 ). The bond angles for the terminal GaCl₃ are 112.87, 114.74, and 114.09°, which are all significantly greater than the 109.5° of tetrahedral geometry. For the title compound, the corresponding angles around Ga2 (Table 1) are much closer to the ideal tetrahedral geometry, which is consistent with [GaCl₄]⁻. In tetraethyl ammonium tetrachloridogallium (Bolte et al., 2023 ), the Cl—Ga—Cl bond angles range from 108.1 to 110.1°. An analogous Lewis acid–base bonding model for the title complex would require a 19 electron ruthenium metal center or that Ga1 carries one formal negative charge, both of which are unlikely.

Table 1
Selected geometric parameters (Å, °)

Ru1—Ga1	2.4575 (2)	Ga2—Cl6	2.1413 (6)
Ga1—Cl2	2.1665 (5)	Ga2—Cl4	2.1456 (6)
Ga1—Cl1	2.1888 (5)	Ga2—Cl5	2.1521 (6)
Ga1—Cl3	2.4619 (5)	Ga2—Cl3	2.2583 (5)

Cl6—Ga2—Cl4	114.95 (3)	Cl6—Ga2—Cl3	110.96 (2)
Cl6—Ga2—Cl5	110.36 (3)	Cl4—Ga2—Cl3	106.43 (2)
Cl4—Ga2—Cl5	109.67 (3)	Cl5—Ga2—Cl3	103.82 (2)

The Ru1—Ga1 bond length of 2.4575 (2) Å for the title compound is very similar to the value of 2.453 (1) Å observed for Ru₂{GaCl₂(THF)}₂(CO)₈ (Harakas & Whittlesey, 1997). The packing is shown in Fig. 2

Figure 2
Crystal packing diagram viewed along the b axis. Hydrogen atoms have been omitted for clarity.

During the work-up of the reaction, the title compound was isolated directly from the toluene solution. It is unknown at this time the role of diphenylsilanediol, if any, in the formation of the title compound. A solid that was insoluble in toluene in the reaction flask was extracted with THF forming an orange solution. This reaction product, which may contain the desired diphenylsiloxane metal cluster, has not yet been fully characterized.

Synthesis and crystallization

All manipulations were carried out under argon using standard Schlenk line techniques. Our previous work (Demmin et al., 2024) demonstrated that silicone-based vacuum grease can contaminate gallium halide reactions. Therefore, PTFE sleeves and non-silicone based vacuum grease were used on all glassware in this experiment. In a 250 ml Schlenk flask, gallium (5.60 g, 80.3 mmole) and GaCl₃ 5.00 g (28.4, mmole) were combined followed by toluene (175 ml). The mixture was heated to reflux for 24 h to produce a solution containing gallium(II) chloride (Ga₂Cl₄), excess gallium was present.

Diphenylsilanediol (0.306 g, 1.41 mmol) was added to a 150 ml Schlenk flask followed by toluene (50 ml). To this flask, 10 ml of the Ga₂Cl₄ stock solution was added via cannula. The dark-gray mixture was refluxed under argon for 72 h resulting in a light-gray mixture. The reaction flask was cooled to 25°C and Ru₃(CO)₁₂ (0.225 g, 0.352 mmol) was then added. The mixture was heated to reflux for an additional 72 h. This resulted in a mixture with a suspended gray solid/gel and colorless solution. The colorless solution was decanted into a 150 ml Schlenk flask via cannula. After standing at 25°C for 10 days, colorless crystals were observed.

A single crystal was coated with NVH oil and mounted on a MiTeGen loop under a stream of argon gas then cooled to −25°C for data collection.

Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[RuGa₂Cl₆(C₇H₈)(CO)₂]
M_r	601.36
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	248
a, b, c (Å)	13.1598 (6), 9.7142 (4), 15.3369 (7)
β (°)	115.257 (1)
V (Å³)	1773.19 (14)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	4.76
Crystal size (mm)	0.36 × 0.34 × 0.31

Data collection
Diffractometer	Bruker D8 Quest Eco, Photon II 7
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.21, 0.32
No. of measured, independent and observed [I > 2σ(I)] reflections	66270, 4424, 4133
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.016, 0.041, 1.09
No. of reflections	4424
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.65, −0.43
Computer programs: APEX3 and SAINT (Bruker, 2019 ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and ShelXle (Hübschle et al., 2011 ).

Structural data

CCDC reference: 2367755

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314624006576/bt4152sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314624006576/bt4152Isup2.hkl

checkCIF report

Computing details top

Dicarbonyl-1κ²C-µ-chlorido-2:3κ²Cl:Cl-pentachlorido-2κ²Cl,3κ³Cl-[1(η⁶)-toluene]digallium(III)ruthenium(I)(Ru—Ga) top

Crystal data top

[RuGa₂Cl₆(C₇H₈)(CO)₂]	F(000) = 1144
M_r = 601.36	D_x = 2.253 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.1598 (6) Å	Cell parameters from 9595 reflections
b = 9.7142 (4) Å	θ = 2.7–28.3°
c = 15.3369 (7) Å	µ = 4.76 mm⁻¹
β = 115.257 (1)°	T = 248 K
V = 1773.19 (14) Å³	Block, clear colourless
Z = 4	0.36 × 0.34 × 0.31 mm

Data collection top

Bruker D8 Quest Eco, Photon II 7 diffractometer	4133 reflections with I > 2σ(I)
Detector resolution: 7.3910 pixels mm^-1	R_int = 0.031
phi and ω scans	θ_max = 28.3°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −17→17
T_min = 0.21, T_max = 0.32	k = −12→12
66270 measured reflections	l = −20→20
4424 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.016	H-atom parameters constrained
wR(F²) = 0.041	w = 1/[σ²(F_o²) + (0.0179P)² + 1.0566P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.002
4424 reflections	Δρ_max = 0.65 e Å⁻³
182 parameters	Δρ_min = −0.43 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ru1	0.24301 (2)	0.66776 (2)	0.55005 (2)	0.02484 (4)
Ga1	0.37587 (2)	0.52947 (2)	0.68455 (2)	0.02795 (5)
Ga2	0.21861 (2)	0.26035 (2)	0.77462 (2)	0.03228 (5)
Cl1	0.53434 (4)	0.47105 (6)	0.68030 (4)	0.04053 (11)
Cl2	0.41255 (5)	0.58077 (6)	0.83247 (3)	0.04424 (12)
Cl3	0.31993 (4)	0.28855 (5)	0.68851 (4)	0.03697 (10)
Cl4	0.09559 (5)	0.42180 (6)	0.73078 (5)	0.05227 (13)
Cl5	0.13673 (5)	0.06499 (6)	0.72620 (5)	0.05478 (14)
Cl6	0.32572 (4)	0.25357 (7)	0.92593 (4)	0.05277 (15)
O1	0.12790 (15)	0.73771 (17)	0.67684 (13)	0.0519 (4)
O2	0.10336 (14)	0.40984 (18)	0.48352 (13)	0.0573 (4)
C1	0.17226 (16)	0.7071 (2)	0.63130 (14)	0.0338 (4)
C2	0.15713 (16)	0.5047 (2)	0.51002 (14)	0.0367 (4)
C3	0.1370 (2)	1.0026 (3)	0.48306 (18)	0.0502 (5)
H3A	0.151190	1.085031	0.454310	0.075000*
H3B	0.148544	1.022284	0.548647	0.075000*
H3C	0.060080	0.972800	0.445748	0.075000*
C4	0.21607 (15)	0.8907 (2)	0.48377 (13)	0.0324 (4)
C5	0.18667 (17)	0.7958 (2)	0.40924 (13)	0.0389 (4)
H5	0.107892	0.790389	0.359964	0.047000*
C6	0.2656 (2)	0.6935 (3)	0.41157 (15)	0.0478 (5)
H6	0.241232	0.618942	0.362932	0.057000*
C7	0.37233 (19)	0.6881 (2)	0.48817 (17)	0.0458 (5)
H7	0.423488	0.610611	0.493398	0.055000*
C8	0.40090 (17)	0.7834 (2)	0.56321 (16)	0.0432 (5)
H8	0.471964	0.772111	0.622005	0.052000*
C9	0.32405 (16)	0.8811 (2)	0.56150 (14)	0.0371 (4)
H9	0.340902	0.937264	0.619916	0.044000*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ru1	0.02522 (6)	0.02903 (7)	0.02071 (6)	−0.00104 (5)	0.01024 (5)	0.00055 (5)
Ga1	0.02861 (9)	0.03056 (10)	0.02508 (9)	0.00314 (7)	0.01183 (7)	0.00206 (7)
Ga2	0.03015 (10)	0.03326 (11)	0.03336 (10)	−0.00027 (8)	0.01347 (8)	0.00417 (8)
Cl1	0.0333 (2)	0.0472 (3)	0.0458 (3)	0.00639 (19)	0.0213 (2)	0.0039 (2)
Cl2	0.0559 (3)	0.0468 (3)	0.0281 (2)	0.0091 (2)	0.0161 (2)	−0.00377 (19)
Cl3	0.0476 (2)	0.0293 (2)	0.0424 (2)	−0.00163 (19)	0.0273 (2)	0.00116 (18)
Cl4	0.0467 (3)	0.0490 (3)	0.0610 (3)	0.0157 (2)	0.0228 (3)	0.0080 (3)
Cl5	0.0554 (3)	0.0405 (3)	0.0623 (3)	−0.0155 (2)	0.0192 (3)	0.0040 (3)
Cl6	0.0389 (2)	0.0864 (4)	0.0323 (2)	0.0041 (3)	0.0145 (2)	0.0060 (3)
O1	0.0721 (11)	0.0459 (9)	0.0607 (10)	0.0051 (8)	0.0503 (9)	0.0003 (8)
O2	0.0500 (9)	0.0449 (9)	0.0626 (10)	−0.0152 (8)	0.0103 (8)	−0.0092 (8)
C1	0.0408 (9)	0.0295 (9)	0.0349 (9)	0.0002 (7)	0.0198 (8)	0.0036 (7)
C2	0.0334 (9)	0.0387 (10)	0.0334 (9)	−0.0019 (8)	0.0099 (7)	−0.0010 (8)
C3	0.0545 (13)	0.0464 (12)	0.0567 (14)	0.0116 (10)	0.0304 (11)	0.0103 (10)
C4	0.0365 (9)	0.0339 (9)	0.0302 (8)	−0.0027 (7)	0.0175 (7)	0.0051 (7)
C5	0.0422 (10)	0.0474 (11)	0.0233 (8)	−0.0055 (9)	0.0101 (7)	0.0060 (8)
C6	0.0754 (15)	0.0475 (12)	0.0321 (10)	−0.0045 (11)	0.0342 (11)	−0.0027 (9)
C7	0.0519 (12)	0.0497 (12)	0.0532 (12)	0.0122 (10)	0.0392 (11)	0.0147 (10)
C8	0.0308 (9)	0.0520 (12)	0.0473 (11)	−0.0053 (9)	0.0172 (8)	0.0101 (10)
C9	0.0371 (9)	0.0378 (10)	0.0343 (9)	−0.0111 (8)	0.0133 (8)	0.0000 (8)

Geometric parameters (Å, º) top

Ru1—C1	1.8856 (19)	Ga2—Cl4	2.1456 (6)
Ru1—C2	1.890 (2)	Ga2—Cl5	2.1521 (6)
Ru1—C6	2.2803 (19)	Ga2—Cl3	2.2583 (5)
Ru1—C7	2.2834 (19)	O1—C1	1.125 (2)
Ru1—C8	2.294 (2)	O2—C2	1.127 (3)
Ru1—C9	2.3027 (19)	C3—C4	1.502 (3)
Ru1—C5	2.3223 (19)	C4—C5	1.389 (3)
Ru1—C4	2.3536 (19)	C4—C9	1.415 (3)
Ru1—Ga1	2.4575 (2)	C5—C6	1.426 (3)
Ga1—Cl2	2.1665 (5)	C6—C7	1.396 (3)
Ga1—Cl1	2.1888 (5)	C7—C8	1.398 (3)
Ga1—Cl3	2.4619 (5)	C8—C9	1.379 (3)
Ga2—Cl6	2.1413 (6)

C1—Ru1—C2	89.37 (9)	Cl2—Ga1—Cl1	107.54 (2)
C1—Ru1—C6	152.94 (9)	Cl2—Ga1—Ru1	120.934 (17)
C2—Ru1—C6	94.99 (9)	Cl1—Ga1—Ru1	117.546 (16)
C1—Ru1—C7	157.35 (9)	Cl2—Ga1—Cl3	97.36 (2)
C2—Ru1—C7	112.70 (9)	Cl1—Ga1—Cl3	93.035 (19)
C6—Ru1—C7	35.62 (9)	Ru1—Ga1—Cl3	115.292 (15)
C1—Ru1—C8	121.78 (9)	Cl6—Ga2—Cl4	114.95 (3)
C2—Ru1—C8	146.39 (9)	Cl6—Ga2—Cl5	110.36 (3)
C6—Ru1—C8	63.59 (9)	Cl4—Ga2—Cl5	109.67 (3)
C7—Ru1—C8	35.56 (9)	Cl6—Ga2—Cl3	110.96 (2)
C1—Ru1—C9	96.35 (8)	Cl4—Ga2—Cl3	106.43 (2)
C2—Ru1—C9	166.51 (8)	Cl5—Ga2—Cl3	103.82 (2)
C6—Ru1—C9	74.46 (8)	Ga2—Cl3—Ga1	112.77 (2)
C7—Ru1—C9	63.31 (8)	O1—C1—Ru1	175.86 (18)
C8—Ru1—C9	34.91 (8)	O2—C2—Ru1	177.7 (2)
C1—Ru1—C5	117.03 (8)	C5—C4—C9	118.47 (18)
C2—Ru1—C5	103.73 (8)	C5—C4—C3	121.72 (19)
C6—Ru1—C5	36.09 (8)	C9—C4—C3	119.81 (19)
C7—Ru1—C5	64.28 (8)	C5—C4—Ru1	71.49 (11)
C8—Ru1—C5	74.78 (7)	C9—C4—Ru1	70.35 (11)
C9—Ru1—C5	62.79 (7)	C3—C4—Ru1	130.19 (13)
C1—Ru1—C4	94.20 (7)	C4—C5—C6	119.83 (19)
C2—Ru1—C4	132.21 (8)	C4—C5—Ru1	73.96 (11)
C6—Ru1—C4	63.40 (8)	C6—C5—Ru1	70.35 (11)
C7—Ru1—C4	75.08 (7)	C7—C6—C5	120.5 (2)
C8—Ru1—C4	63.34 (7)	C7—C6—Ru1	72.31 (11)
C9—Ru1—C4	35.37 (7)	C5—C6—Ru1	73.56 (11)
C5—Ru1—C4	34.55 (7)	C6—C7—C8	119.2 (2)
C1—Ru1—Ga1	86.05 (6)	C6—C7—Ru1	72.07 (12)
C2—Ru1—Ga1	85.82 (6)	C8—C7—Ru1	72.63 (11)
C6—Ru1—Ga1	120.86 (7)	C9—C8—C7	120.2 (2)
C7—Ru1—Ga1	90.38 (6)	C9—C8—Ru1	72.89 (11)
C8—Ru1—Ga1	84.29 (6)	C7—C8—Ru1	71.81 (12)
C9—Ru1—Ga1	106.70 (5)	C8—C9—C4	121.73 (19)
C5—Ru1—Ga1	154.66 (5)	C8—C9—Ru1	72.20 (12)
C4—Ru1—Ga1	141.95 (5)	C4—C9—Ru1	74.28 (11)

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