to a suspension of InCl3 (1.55 g, 7.02 mmol) in Et2O (20 mL) at ca. 278 °C.
The mixture was stirred at ca. 278° C (1 h), before warming to ca. 20 °C,
and stirred overnight. The solvent was removed and the residue was
extracted with hexane (100 mL), and filtered (Celite). The pale yellow
solution was concentrated to ca. 20 mL and heated to redissolve the
precipitates. Standing at ca. 20 °C afforded colorless crystalline 2, 3.74 g,
80%. Mp 160 °C opaque, 226 °C sweats, 236–238 °C melt. Anal. calc.
(found) for C72H98Cl4In2: C, 64.78 (64.01), H, 7.39 (8.2)%. IR nIn–Cl 335s
br cm21; 1H NMR (300 MHz, C6D6) d 1.05 [d, 24H, p-CH(CH3)2, 3JHH 6.6
Hz], 1.36 [d, 24H, o-CH(CH3)2, 3JHH 6.9 Hz], 1.44 [d, 24H, o-CH(CH3)2,
3JHH 6.9 Hz], 2.90 [m, 12H, p-CH(CH3)2 + o-CH(CH3)2, 3JHH 6.6 Hz], 7.11
3
(t, 2H, p-C6H3, JHH 7.5 Hz), 7.21 (s, 8H, m-Trip), 7.22 (d, 4H, m-C6H3,
3JHH 13.2 Hz); 13C{1H} NMR (75 MHz, C6D6) d 23.1 [p-CH(CH3)2], 24.4
[o-CH(CH3)2], 26.2 [o-CH(CH3)2], 31.0 [o-CH(CH3)2], 34.9 [p-
CH(CH3)2], 121.8 (m-Trip), 128.9 (p-C6H3), 129.8 (m-C6H3), 138.5 (ipso-
Trip), 147.1 (p-Trip), 148.1 (o-Trip), 149.8 (o-C6H3), ipso C resonance not
observed. 3: H2O (33 mL, 1.85 mmol) was added to 1b (1.15 g, 1.85 mmol)
in THF (40 mL) at ca. 0 °C and stirred (2 d). The solvent was removed under
reduced pressure and the residue was extracted with C6H6 (40 mL), filtered
(Celite) and concentrated to ca. 10 mL. The solution was cooled to ca. 5 °C
(2 weeks) to afford 3 as colorless crystals, 1.08 g, 90%. Anal. calc. (found)
for C72H100Cl2Ga2O2: C, 71.59 (72.31); H, 8.34 (8.62)%. Mp 215 °C
sweats, 227–229 °C melt. IR nOH 3440br, 3200br, nGa–Cl 380s, 330s br
cm21; 1H NMR (300 MHz, CDCl3) d 0.94 [d, 24H, o-CH(CH3)2, 3JHH 6.9
Hz], 1.13 [d, 24H, o-CH(CH3)2, 3JHH 6.6 Hz], 1.17 [d, 24H, p-CH(CH3)2,
3JHH 6.75 Hz], 2.58 [sept, 8H, o-CH(CH3)2, 3JHH 6.75 Hz], 2.815 (sept, 4H,
p-CH(CH3)2, 3JHH 6.9 Hz], 4.00 (s, br 2H, OH), 6.97 (s, 8H, m-Trip), 7.10
(d, 4H, m-C6H3, 3JHH 7.5 Hz), 7.31 (t, 2H, p-C6H3, 3JHH 7.5 Hz); 13C{1H}
NMR (75 MHz, CDCl3) d 22.6 [p-CH(CH3)2], 24.1 [o-CH(CH3)2], 25.7 [o-
CH(CH3)2], 30.5 [o-CH(CH3)2], 34.4 [p-CH(CH3)2], 120.9 (m-Trip), 127.9
(p-C6H3), 128.9 (m-C6H3), 137.8 (ipso-Trip), 146.6 (p-Trip), 147.4 (o-
Trip), 149.2 (o-C6H3), ipso C resonance not observed.
Fig. 3 Drawing of the structure of 3 (30% probability). H atoms not shown.
Selected bond lengths (Å) and angles (°): Ga(1)–C(1) 1.949(5), Ga(1)–O(1)
1.932(4), Ga(1)–(O1A) 1.906(4), Ga(1)–Cl(1) 2.1465(19); C(1)–Ga(1)–
Cl(1) 126.23(17), Ga(1)–O(1)–Ga(1A) 99.94(19), O(1A)–Ga(1)–Cl(1)
104.33(14).
M–OH and M–Cl (M = Ga, In) bonds, the contamination of the
m–Cl2 positions by OH2 ions is 50% which is sufficient to
produce the apparent ‘dimerization’; (c) the M–Cl distances in
both 1b and 2 are normal, and there is no shortening in the
bridging In–Cl distance which is ca. 0.29 Å longer than the
terminal In–Cl bond.
We note that the hydrolysis of related organogallium
compounds to give Ga–OH products has been investigated in
detail,8,10 and the susceptibility of 1b and 2 to hydrolysis agrees
with these studies. The ability of OH2 ligands to occupy Cl–
sites bears some similarity to the bond stretch isomerism
controversy where ‘short’ M–Cl (or ‘long’ M–O) bonds were
shown to be a result of occupancy of the same site by different
percentages of the O or Cl atoms rather than a new type of
bonding isomerism.11
§ Crystal data at 130 K for 1b and 299 K for 2 and 3, with Mo-Ka (l =
0.71073 Å) radiation: 1b: C36H49Cl2Ga, M = 622.37, orthorhombic, space
group Pbcm, a = 11.069(2), b = 12.170(2), c = 25.275(5) Å, V =
3404.8(12) Å3, Z = 4, Dc = 1.214 Mg m23, m = 0.987 mm21, scan type
w scans, q range 1.6–22.50°. GoF on F2 0.999 for 2287 unique observed
data and 190 parameters, R1 = 0.0676, wR2 = 0.1096. 2: C72H98Cl4In2, M
= 1334.94, orthorhombic, space group Cmca, a = 25.6540(13), b =
21.2270(11), c = 12.7609(6) Å, V = 6949.0(6) Å3, Z = 4, Dc = 1.276 Mg
m23, m = 0.855 mm21, scan type f and w scans, q range 1.92–29.00°. GOF
on F2 1.058 for 4706 unique observed data and 203 parameters, R1
0.0418, wR2 0.0691. 3·2C6H6: C84H112Cl2Ga2O2, M 1364.08,
=
=
=
monoclinic, space group P21/c, a = 14.2605(10), b = 15.9037(10), c =
18.0905(12) Å, b = 108.613(2)°, V = 3888.2(4) Å3, Z = 2, Dc = 1.165 Mg
m23, m = 0.805 mm21, scan type f and w scans, q range 1.75–22.50°. GOF
Notes and references
on F2 1.017 for 5074 unique observed data and 419 parameters, R1
0.0620, wR2 = 0.1037.
=
† The effective ionic radius of four coordinate Ga3+ is 0.47 Å and that of
In3+ is 0.62 Å: R. D. Shannon, Acta Crystallogr., Sect. A, 1976, 32, 751.
‡ Experimental: 1a: under anaerobic and anhydrous conditions, 2,6-Trip2-
H3C6Li·OEt2 (7.90 g, 14 mmol) in Et2O (40 mL) at 0 °C was added
dropwise (0.5 h) to freshly sublimed GaCl3 (2.47 g, 14 mmol) in Et2O (20
mL) at ca. 278 °C. The mixture was stirred at ca. 278 °C (3 h) before
warming to ca. 20 °C. After stirring for 2 d, the solvent was removed and
the residue was extracted with hexane (80 mL) and filtered (Celite).
Concentration to incipient crystallization (ca. 40 mL) and cooling to ca.
225 °C yielded colorless crystals of 1a, 7.60 g, 78%. Anal. calc. (found) for
C40H59Cl2GaO: C, 68.98 (68.53), H, 8.54 (8.91)%. 1H NMR (300 MHz,
crystallographic files in .cif format.
1 J. Su, X.-W. Li, and G.H. Robinson, Chem. Commun., 1998, 2015.
2 G. H. Robinson, X.-W. Li and W. T. Pennington, J. Organomet. Chem.,
1995, 501, 399; R. C. Crittendon, X.-W. Li, J. Su and G. H. Robinson,
Organometallics, 1997, 16, 2443.
3 E.g. (a) O. T. Beachley, R. B. Hallock, H. M. Zhang and J. L. Atwood,
Organometallics, 1985, 4, 1675; (b) R. D. Schluter, H. S. Isom, A. H.
Cowley, D. A. Atwood, R. A. Jones, F. Olbrich, S. Corbelin and R. J.
Lagow, Organometallics, 1994, 13, 4058; (c) M. B. Power, W. M.
Cleaver, A. W. Apblett, A. R. Barron and J. W. Ziller, Polyhedron,
1992, 11, 477; (d) M. F. Self, A. T. McPhail, L. J. Jones III, R. L. Wells
and J. C. Huffman, Polyhedron, 1994, 13, 199.
3
C6D6) d 0.82 [t, 6H, (CH3CH2)2O], 1.15 [d, 12H, o-CH(CH3)2, JHH 6.6
Hz], 1.29 [d, 12H, p-CH(CH3)2, 3JHH 6.9 Hz], 1.53 [d, 12H, o-CH(CH3)2,
3JHH 6.0 Hz], 2.88 [sept, 2H, p-CH(CH3)2, 3JHH 6.6 Hz], 3.14 [q, 4H + 4H,
(CH3CH2)2O + o-CH(CH3)2, JHH 6.9 Hz], 7.19–7.28 [m, 7H, p-C6H3, m-
4 R. J. Wehmschulte, W. J. Grigsby, B. Schiemenz, R. A. Bartlett and
P. P. Power, Inorg. Chem., 1996, 35, 6694.
Trip (7.24, s), m-C6H3]; 13C{1H} NMR (75 MHz, C6D6)
d 14.3
[(CH3CH2)2O], 23.1 [p-CH(CH3)2], 24.4 [o-CH(CH3)2], 26.2 [o-
CH(CH3)2], 31.1 [o-CH(CH3)2], 34.8 [p-CH(CH3)2], 66.1 [(CH3CH2)2O)],
121.0 (m-Trip), 128.2 (p-C6H3), 130.1 (m-C6H3), 138.8 (ipso-Trip), 147.4
(p-Trip), 147.8 (o-Trip), 148.8 (br, o-C6H3), the ipso C resonance was not
observed. 1b: 1a (6.5 g, 0.93 mmol) in hexane (100 mL) was concentrated
to ca. 50 mL. The precipitates were redissolved by heating and 1b
crystallized on standing at ca. 20 °C. Yield 5.0 g, 87%. Mp 230 °C sweats,
244 °C partial melt, 258–260 °C complete melt. Anal. calc. (found) for
C36H49Cl2Ga: C, 69.47 (68.90), H, 7.94 (8.11)%. IR nGa–Cl 400s, 330s br
5 B. Schiemenz and P. P. Power, Organometallics, 1996, 15, 958.
6 (a) M. A. Petrie, P. P. Power, H. V. Rasika Dias, K. Ruhlandt-Senge,
K. M. Waggoner and R. J. Wehmschulte, Organometallics, 1993, 12,
1086; (b) S. Schulz, S. Pusch, E. Pohl, S. Dielkus, R. Herbst-Irmer, A.
Meller and H. W. Roesky, Inorg. Chem., 1993, 32, 3343.
7 R. D. Schluter, H. S. Isom, A. H. Cowley, D. A. Atwood, R. A. Jones,
F. Olbrich, S. Corbelin and R. J. Lagow, Organometallics, 1994, 13,
4058.
8 J. Storre, A. Klemp, H. W. Roesky, H.-G. Schmidt, M. Noltemeyer, R.
Fleischer and D. Stalke, J. Am. Chem. Soc., 1996, 118, 1380.
9 W. Uhl, I. Hahn, M. Koch and M. Layh, Inorg. Chim. Acta, 1996, 249,
33.
1
3
cm21; H NMR (300 MHz, C6D6) d 1.06 [d, 12H, o-CH(CH3)2, JHH 6.9
Hz], 1.26 [d, 12H, p-CH(CH3)2, 3JHH 6.9 Hz], 1.42 [d, 12H, o-CH(CH3)2,
3JHH 6.9 Hz], 2.84 [sept, 2H, p-CH(CH3)2, 3JHH 6.9 Hz], 2.94 [sept, 4H, o-
3
CH(CH3)2, JHH 6.9 Hz], 7.17–7.24 [m, 7H, p-C6H3, m-Trip (7.21, s), m-
10 C. Schnitter, H. W. Roesky, T. Albers, H.-G. Schmidt, C. Ropken, E.
Parisini and G. M. Sheldrick, Chem. Eur. J., 1997, 3, 1783.
11 G. Parkin, Acc. Chem. Res., 1992, 25, 455; G. Parkin, Chem. Rev., 1993,
93, 887.
C6H3]; 13C{1H} NMR (75 MHz, C6D6) d 22.5 [p-CH(CH3)2], 24.3 [o-
CH(CH3)2], 26.3 [o-CH(CH3)2], 31.1 [o-CH(CH3)2], 34.8 [p-CH(CH3)2],
121.8 (m-Trip), 128.3 (p-C6H3), 129.1 (m-C6H3), 137.8 (ipso-Trip), 146.8
(p-Trip), 147.3 (o-Trip), 150.3 (o-C6H3), 171.6 (ipso-C6H3). 2: A solution
of 2,6-Trip2H3C6Li·OEt2 (3.95 g, 7.02 mmol) in Et2O (40 mL) was added
Communication 9/04212A
1806
Chem. Commun., 1999, 1805–1806