Insertion of strongly electron withdrawing cyanoolefins into the C-H bond in pentamethylcyclopentadienyl-rhodium(III) and -iridium(III) complexes containing P-O or P-O-O′ coordinations

Article abstract of DOI:10.1021/om000781c

Complexes, Cp*MCl(MDMPP-P,O) (1a: M = Rh, 1b: M = Ir; Cp* = η⁵-C₅Me₅; MDMPP-P,O = PPh₂(C₆H₃-2-O-6-MeO)) readily react with tcne or tcnq to form the 1:1 adducts [Cp*MCl(MDMPP-P,O)(ol)] (ol = tcne (c), tcnq (d)) (3ac: M = Rh, ol = tcne; 3bc: M = Ir, ol = tcne; 4ad: M = Rh, ol = tcnq; 4bd: M = Ir, ol = tcnq), derived from insertion of cyanoolefins into the C-H bond adjacent to the metal-O bond. Complex Cp*Ir(TDMPP-P,O,O′) 2b (TDMPP-P,O,O′ = P{C₆H₃-2,6-(MeO)₂}(C₆H₃-2-O-6-MeO)₂) bearing a (P,O,O′) coordination was treated with 1 equiv of tcne, tcnq, or Me₂-tcnq (e) to give the products in which one molecule of cyanoolefin was inserted, [Cp*Ir(TDMPP-P,O,O′)(ol)] (5bc: ol = tcne; 6bd: ol = tcnq; 6be: ol = Me₂-tcnq). Reactions with 2 equiv of cyanoolefin gave the products [Cp*Ir(TDMPP-P,O,O′)(ol)₂] (7bc: ol = tcne; 8bd: ol = tcnq), in which insertion occurred at two C-H positions adjacent to the Ir-O bonds. Structural data for 3ac, 3bc, 4ad, 5bc, and 7bc are described.

Full text of DOI:10.1021/om000781c

266
Organometallics 2001, 20, 266-272
In ser tion of Str on gly Electr on With d r a w in g
Cya n oolefin s in to th e C-H Bon d in
P en ta m eth ylcyclop en ta d ien yl-Rh od iu m (III) a n d
-Ir id iu m (III) Com p lexes Con ta in in g P -O or P -O-O′
Coor d in a tion s
Yasuhiro Yamamoto,*,† Xiao-Hong Han,† Saho Nishimura,†
Ken-ichiro Sugawara,† Nobumichi Nezu,† and Tomoaki Tanase‡,§
Department of Chemistry, Faculty of Science, Toho University, Miyama,
Funabashi, Chiba, 274-8510 J apan, and Department of Chemistry, Faculty of Science,
Nara Women’s University, Kitauoya-Higashimachi, Nara, 630-8285 J apan
Received September 12, 2000
Complexes, Cp*MCl(MDMPP-P,O) (1a : M ) Rh, 1b: M ) Ir; Cp* ) η5-C5Me5; MDMPP-
P,O ) PPh2(C6H3-2-O-6-MeO)) readily react with tcne or tcnq to form the 1:1 adducts
[Cp*MCl(MDMPP-P,O)(ol)] (ol ) tcne (c), tcnq (d )) (3a c: M ) Rh, ol ) tcne; 3bc: M ) Ir,
ol ) tcne; 4a d : M ) Rh, ol ) tcnq; 4b d : M ) Ir, ol ) tcnq), derived from insertion of
cyanoolefins into the C-H bond adjacent to the metal-O bond. Complex Cp*Ir(TDMPP-
P,O,O′) 2b (TDMPP-P,O,O′ ) P{C6H3-2,6-(MeO)2}(C6H3-2-O-6-MeO)2) bearing a (P,O,O′)
coordination was treated with 1 equiv of tcne, tcnq, or Me2-tcnq (e) to give the products in
which one molecule of cyanoolefin was inserted, [Cp*Ir(TDMPP-P,O,O′)(ol)] (5bc: ol ) tcne;
6bd : ol ) tcnq; 6be: ol ) Me2-tcnq). Reactions with 2 equiv of cyanoolefin gave the products
[Cp*Ir(TDMPP-P,O,O′)(ol)2] (7bc: ol ) tcne; 8bd : ol ) tcnq), in which insertion occurred
at two C-H positions adjacent to the Ir-O bonds. Structural data for 3a c, 3bc, 4a d , 5bc,
and 7bc are described.
In tr od u ction
C5Me5; MDMPP-P,O ) PPh2(C6H3-2-O-6-MeO), BD-
MPP-P,O ) PPh{C6H3-2,6-(MeO)6}(C6H3-2-O-6-MeO),
TDMPP-P,O,O′ ) P{C6H3-2,6-(MeO)6}(C6H3-2-O-6-MeO)2)
with (P,O) or (P,O,O′) chelating phosphines, respec-
tively. When complexes Cp*MCl(MDMPP-P,O) (1a : M
) Rh; 1b: M ) Ir) were treated with 1-alkyne or
disubstituted alkyne in the presence of KPF6 or NaPF6,
novel single or double insertion of alkyne into the Rh-O
or P-C bond gave six- or seven-membered metalla-
cycles.7,8 Reaction of Cp*RhCl(BDMPP-P,O) with HCt
CC6H4-4-R (R ) COOMe, NO2) underwent unprec-
edented transannular addition between the rhodium
atom and ipso-carbon atom of the phenyl group of the
phosphine ligand.8
During the research on interactions of the aforemen-
tioned complexes with small molecules such as olefins
and alkynes, we found that 1 or Cp*Ir(TDMPP-P,O,O′)
2b (M ) Ir) reacted with electron-deficient olefins such
as tetracyanoethylene (tcne), 7,7,8,8,-tetracyano-p-quin-
odimethane (tcnq), and 1,5-dimethyl-7,7,8,8-tetracyano-
p-quinodimethane (Me2-tcnq) (e), which inserted into
weakly activated C-H bonds on the phenyl ring of the
phosphine ligand. These insertion reactions into a C-H
bond on the ligand showed novel reactivity of electron-
deficient olefins and are considered as an electrophilic
Aromatic phosphines bearing methoxy groups at the
2- and 6-positions of the phenyl groups exhibit high
basicity and nucleophilicity.1-3 Recently we reported
that one or two of the ortho-methoxy groups in (2,6-
dimethoxyphenyl)diphenylphosphine (MDMPP), bis(2,6-
dimethoxyphenyl) phenylphosphine (BDMPP), and tris-
(2,6-dimethoxyphenyl)phenylphosphine (TDMPP) were
demethylated in the reactions with bis[dichloro(η6-
arene)ruthenium(II)] or bis[dichloro(η5-pentamethylcy-
clopentadienyl)rhodium(III) (or iridium(III))] to give (η6-
arene)RuCl(MDMPP-P,O), (η6-arene)RuCl(TDMPP-P,O)4
(arene ) p-cymene, 1,2,3-Me3C6H3, 1,3,5-Me3C6H3, and
C6Me6), Cp*MCl(MDMPP-P,O), Cp*MCl(BDMPP-P,O),
and Cp*M(TDMPP-P,O,O′) (M ) Rh5 and Ir;6 Cp* ) η5-
* Corresponding author. Fax:
yamamoto@chem.sci.toho-u.ac.jp.
† Toho University.
+81-474-75-1855. E-mail:
‡ Nara Women’s University.
§ E-mail: tanase@cc.nara-wu.ac.jp.
(1) (a) Wada, M.; Higashimura, A. J . Chem. Soc., Chem. Commun.
1984, 482. (b) Wada, M.; Higashimura, A.; Tsuboi, A. J . Chem. Res.
Synp. 1985, 38. Wada, M.; Higashimura, A.; Tsuboi, A. J . Chem. Res.
Miniprint 1985, 467.
(2) Wada, M.; Tsuboi, A. J . Chem. Soc., Perkin Trans. 1987, 1, 151.
(3) (a) Wada, M.; Tsuboi, A.; Nishimura, K.; Erabi, T. Nippon Kafaku
Kaishi 1987, 1284. (b) Kurosawa, H.; Tsuboi, A.; Kawasaki, Y.; Wada,
M. Bull. Chem. Soc. J pn. 1987, 60, 3563.
(4) (a) Yamamoto, Y.; Sato, R.; Ohshima, M.; Matsuo, F.; Sudoh, C.
J . Organomet. Chem. 1995, 489, C68. Yamamoto, Y.; Sato, R.; Matsuo,
F.; Sudoh, C.; Igoshi, T. Inorg. Chem. 1996, 35, 2329. (b) Yamamoto,
Y.; Tanase, T.; Sudoh, C.; Turuta, T. J . Organomet. Chem. 1998, 569,
29.
(6) Yamamoto, Y.; Kawasaki, K.; Nishimura, S. J . Organomet.
Chem. 1999, 587, 49.
(7) Yamamoto, Y.; Han, X.-H.; Ma, J .-F. Angew. Chem. 2000, 113;
Angew. Chem., Int. Ed. 2000, 39, 1965.
(8) Yamamoto, Y.; Sugawara, K. J . Chem. Soc., Dalton Trans. 2000,
2896.
(5) Han, X.-H.; Yamamoto, Y. J . Organomet. Chem. 1998, 561, 157.
10.1021/om000781c CCC: $20.00 © 2001 American Chemical Society
Publication on Web 12/08/2000

Insertion of Cyanoolefins into C-H Bond
Organometallics, Vol. 20, No. 2, 2001 267
Sch em e 1. Rea ction s of 1 or 2 w ith Str on gly Electr on With d r a w in g Cya n oolefin s
substitution on a weakly activated phenyl ring. Similar
insertions of electron-deficient olefins have been docu-
mented by Onitsuka et al.: square-planar complexes,
2-furanylplatinum chloride, bearing PMe3, PEt3, or
PMe2Ph underwent insertion of tcne or tcnq into the
C-H bond at the 3- or 5-position.9
A preliminary account of this work has been pub-
lished.10
Resu lts a n d Discu ssion
When tcne (c) was added to 1a or 1b in CH2Cl2 at
room temperature, the solution became brown or yellow.
In each case, the 1:1 adducts, formulated as [Cp*MCl-
(MDMPP-P,O)(tcne)] (3a c: M ) Rh; 3bc: M ) Ir), were
isolated on the basis of fast atom bombardment (FAB)
mass spectrometry (Scheme 1). In the IR spectrum of
3a c, a very weak CtN stretching frequency appeared
at 2250 cm-1, which is higher in energy than those of
free tcne (2207 cm-1) and π-complexes (2170-2235
cm-1).11 However, no infrared signal was observed for
3bc, as bands in the νCN region are extremely weak. In
the 1H NMR spectra of 3, three characteristic reso-
nances around δ 1.50(d), 3.50(s), and 6.40(s) were
assigned to the Cp*, methoxy, and HC(CN)2 protons,
F igu r e 1. Perspective ORTEP view of the molecular
structure of 3a c‚CH2Cl2 with thermal ellipsoids drawn at
50% probability. A CH2Cl2 molecule was omitted for clarity.
respectively. The structures of 3a c and 3bc were
determined by X-ray crystal structure analyses (Figures
1 and 2). Crystallographic data are shown in Table 1.
Selected bond lengths and angles are listed in Tables 2
and 3. Complex 3a c contains a CH2Cl2 molecule as a
crystal solvent. The tcne molecule was inserted into the
C-H bond adjacent to the metal-O σ-bond. The CH-
(CN)2 and C(CN)2R groups adopt a staggered conforma-
tion, as torsion angles of the C(27)-C(30)-C(31)-C(34)
and C(27)-C(30)-C(31)-C(35) bonds are 168.8(5)° and
-67.1(6)° for 3a c and 170.6(7)° and -64.6(8)° for 3bc,
(9) Onitsuka, K.; Urayama, H.; Sonogashira, K.; Ozawa, F. Chem.
Lett. 1995, 1019.
(10) Yamamoto, Y.; Han, X.-H.; Sugawara, K.; Nishimura, S. Angew.
Chem. 1999, 112, 1318; Angew. Chem., Int. Ed. 1999, 38, 1242.
(11) For example, Fatiadi, A. J . Synthesis 1987, 959, and references
therein.

268 Organometallics, Vol. 20, No. 2, 2001
Yamamoto et al.
Ta ble 1. Cr ysta llogr a p h ic Da ta for [Cp *Rh Cl(MDMP P -P ,O)(tcn e)‚CH2Cl2], 3a ‚CH2Cl2,
[Cp *Ir Cl(MDMP P -P ,O)(tcn e)], 3bc, [(Cp *Rh Cl(MDMP P -P ,O)(tcn q)], 4a d , [Cp *Ir (TDMP P -P ,O,O′)(tcn e)],
5bc‚H2O, a n d [Cp *Ir (TDMP P -P ,O,O′)(tcn e)2], 7bc‚0.5CH2Cl2
3a c‚CH2Cl2
3bc
4a d
5bc‚H2O
7bc‚0.5CH2Cl2
formula
mol wt
C36H33N4O2PCl3Rh
793.92
C35H31N4O2PClIr
788.3
C41H35N4O2PClRh
785.1
C38H36N4O6PIr
867.92
C44.5H37N8O6PClIr
1038.48
cryst syst
space group
a, Å
b, Å
c, Å
monoclinic
P21/c (No. 14)
12.047(3)
19.293(3)
16.089(3)
94.33(2)
monoclinic
P21/n (No. 14)
12.123(5)
14.314(5)
20.407(3)
95.34(2)
3525(1)
monoclinic
P21/n (No. 14)
13.70(1)
19.076(7)
15.965(10)
101.31(6)
4092(4)
monoclinic
P21/c (No. 14)
16.601(8)
12.808(6)
18.151(6)
95.31(3)
3842(2)
monoclinic
P21/a (No. 14)
19.185(4)
11.631(3)
20.056(
â, deg
95.92(1)
4451(1)
V, Å3
3728(1)
Z
4
4
4
4
4
d(calc), g/cm3
µ, cm-1
1.414
7.51
6790
1.504
39.53
6485
1.274
5.58
7450
1.500
35.74
7099
1.549
31.60
7784
no. of reflns (θ < 50°)
no. of data used
no. of variables
6551 (I > -10.0σ(I))
4487 (I > 3.0σ(I))
2941 (I > 4.0σ(I))
6747 (I > -10.0σ(I))
5378 (I > 2.0σ(I))
409
397
397
460
569
R; Rw
%
0.122; 0.188a
0.065 (4024)
1.22
0.028; 0.034b
0.055; 0.080b
0.162; 0.183a
0.061 (3185)
0.97
0.048; 0.057b
R1 (reflns)
GOFc
1.33
2.28b
1.38
R ) ∑(Fo - Fc2)/∑Fo2, Rw ) [∑w(Fo - Fc2)2/∑w(Fo2)2]0.5 and R1 ) ∑||Fo| - |Fc||/∑|Fo| for I > 2.0σ(I). R ) ∑||Fo| - |Fc||/∑|Fo| and Rw
a
2
2
b
2
0.5
) [∑w(|Fo| - |Fc|)2/∑wFo
]
.
c GOF ) [∑w(|Fo| - |Fc|)2/(Nobs - Nparm)]1/2
.
Ta ble 2. Selected Bon d Len gth s (Å) a n d An gles (d eg) for 3a c‚CH2Cl2
Rh(1)-Cl(1)
P(1)-C(23)
O(1)-C(24)
C(30)-C(32)
C(33)-N(2)
C(31)-C(35)
2.412(2)
1.807(8)
1.352(9)
1.47(1)
1.14(1)
1.47(1)
Rh(1)-P(1)
C(23)-C(28)
C(27)-C(30)
C(32)-N(1)
C(31)-C(34)
C(35)-N(4)
2.323(2)
1.399(10)
1.51(1)
1.13(1)
1.45(1)
1.14(1)
Rh(1)-O(2)
O(2)-C(28)
C(30)-C(31)
C(30)-C(33)
C(34)-N(3)
2.084(5)
1.324(8)
1.58(1)
1.49(1)
1.13(1)
Cl(1)-Rh(1)-P(1)
Rh(1)-P(1)-C(23)
Rh(1)-O(2)-C(28)
C(27)-C(30)-C(32)
C(31)-C(30)-C(33)
C(30)-C(31)-C(35)
C(30)-C(33)-N(2)
91.31(7)
Cl(1)-Ir(1)-O(2)
84.5(1)
112.4(5)
117.2(6)
112.3(6)
106.1(7)
110.9(8)
177(1)
P(1)-Ir(1)-O(2)
80.3(1)
123.8(7)
109.5(6)
108.5(6)
113.4(7)
179.5(10)
177(1)
99.3(2)
117.0(4)
112.5(7)
107.8(7)
109.9(7)
177.5(9)
P(1)-C(23)-C(28)
C(28)-C(27)-C(30)
C(27)-C(30)-C(33)
C(32)-C(30)-C(33)
C(34)-C(31)-C(35)
C(31)-C(34)-N(3)
C(23)-C(28)-O(2)
C(27)-C(30)-C(31)
C(31)-C(30)-C(32)
C(30)-C(31)-C(34)
C(30)-C(32)-N(1)
C(31)-C(35)-N(4)
and Cl(1)‚‚‚C(31) interatomic contacts are 2.84 and 3.63
Å for 3a c and 2.78 and 3.63 Å for 3bc, respectively,
suggesting the presence of a very weak Cl‚‚‚H interac-
tion; this is considered to cause an expansion of the Cl-
M-P bond angle and narrowing of the Cl-M-O angle
in comparison with those for 1a (vide infra).
Complexes 1a and 1b readily reacted with tcnq (d )
to form orange crystals formulated as the 1:1 adduct
(4a d or 4bd ). The IR spectra of 4 showed a CtN
stretching frequency around 2245 cm-1, which is ca. 20
1
cm-1 higher in energy than that for free tcnq. The H
NMR spectra showed three characteristic resonances
around δ1.40 (d), 3.45 (s), and 5.07 (s), assignable to the
Cp*, methoxy, and HC(CN)2 protons, respectively. These
chemical shift values appeared at higher fields than
those for 3; this is a result of the strong electron-
withdrawing ability of the C(CN)2C(CN)2 moiety in 3.
The signal for para-substituted phenyl protons is an AB-
type quartet, suggesting aromatization of the quinone
group. The 31P{1H} NMR spectra showed a doublet at
δ 48.4 (J RhP ) 150.0 Hz) for 4a d and a singlet at δ 28.1
for 4bd , appearing at higher fields than those for 3. In
the crystal structure analysis of 4a d , the bulky C6H4C-
(CN)2H moiety is pointing in the opposite direction as
the Cl ligand, different from the cases in 3, relieving
steric repulsion between two groups (Figure 3 and Table
4). The C(30)-C(31) and C(34)-C(37) bond lengths are
1.54(1) and 1.56(1) Å, respectively, in agreement with
a C-C single bond. The C(30)R(CN)2 and C(37)H(CN)2
F igu r e 2. Perspective ORTEP view of the molecular
structure of 3bc with thermal ellipsoids drawn at 50%
probability.
respectively. The Rh(1)-P(1), Rh(1)-Cl(1), and Rh(1)-
O(1) bond lengths in 3a c are longer than the corre-
sponding bond lengths of 1a .5 The bond distances
around the Ir atom in 3bc are not significantly different
from those of 3a c, but the bond angles are somewhat
narrower than those of the rhodium complex. The Cl-
(1)-M-P(1) angles of 91.3(7)° for 3a c and of 89.99(5)°
for 3bc are wider than the Cl(1)-M-O(2) and P(1)-
M-O(2) bond angles. The C(30)-C(31) bond length is
1.58(1) Å for 3a c and 1.592(7) Å for 3bc, respectively,
in agreement with a C-C single bond. The Cl(1)‚‚‚H(31)

Insertion of Cyanoolefins into C-H Bond
Organometallics, Vol. 20, No. 2, 2001 269
Ta ble 3. Selected Bon d Len gth s (Å) a n d An gles (d eg) for 3bc
Ir(1)-Cl(1)
P(1)-C(23)
O(1)-C(24)
C(30)-C(32)
C(33)-N(2)
C(31)-C(35)
Cl(1)‚‚‚H(31)
2.411(2)
1.813(5)
1.352(6)
1.494(8)
1.127(7)
1.450(9)
2.78
Ir(1)-P(1)
2.311(1)
1.404(7)
1.517(7)
1.116(7)
1.452(8)
1.125(9)
3.63
Ir(1)-O(2)
2.096(3)
1.311(6)
1.592(7)
1.489(8)
1.134(8)
C(23)-C(28)
C(27)-C(30)
C(32)-N(1)
C(31)-C(34)
C(35)-N(4)
Cl(1)‚‚‚C(31)
O(2)-C(28)
C(30)-C(31)
C(30)-C(33)
C(34)-N(3)
Cl(1)-Ir(1)-P(1)
Ir(1)-P(1)-C(23)
Ir(1)-O(2)-C(28)
C(27)-C30-C32
C(31)-C(30)-C(33)
C(30)-C(31)-C(35)
C(30)-C(33)-N(2)
89.99(5)
99.7(2)
Cl(1)-Ir(1)-O(2)
80.88(10)
113.4(3)
116.0(4)
111.6(4)
107.0(5)
110.6(5)
177.6(8)
P(1)-Ir(1)-O(2)
C23-C28-O2
C(27)-C(30)-C31
C(31)-C(30)-C(32)
C(30)-C(31)-C(34)
C(30)-C(32)-N(1)
C(31)-C(35)-N(4)
81.56(9)
P(1)-C(23)-C(28)
C(28)-C(27)-C(30)
C(27)-C(30)-C(33)
C(32)-C(30)-C(33)
C(34)-C(31)-C(35)
C(31)-C(34)-N(3)
122.3(4)
110.1(4()
107.4(4)
112.9(5)
176.3(7)
177.6(8)
117.9(3)
112.0(5)
108.7(5)
110.1(5)
178.3(7)
Ta ble 4. Selected Bon d Len gth s (Å) a n d An gles (d eg) for 4a d
Rh(1)-Cl(1)
2.393(3)
1.800(10)
1.36(1)
1.49(2)
1.14(1)
1.12(2)
Rh(1)-P(1)
C(23)-C(24)
C(25)-C(30)
C(38)-N(1)
C(34)-C(37)
C(37)-C(41)
2.306(3)
1.42(1)
1.54(1)
1.18(2)
1.56(2)
1.47(2)
Rh(1)-O(1)
O(1)-C(24)
C(30)-C(31)
C(30)-C(39)
C(37)-C(40)
C(41)-N(4)
2.085(7)
1.31(1)
1.54(1)
1.48(2)
1.53(2)
1.13(2)
P(1)-C(23)
O(2)-C(28)
C(30)-C(38)
C(39)-N(2)
C(40)-N(3)
phenyl ring (C31-C36)
av 1.35
Cl(1)-Rh(1)-P(1)
Rh(1)-P(1)-C(23)
Rh(1)-O(1)-C(24)
C(25)-C(30)-C(39)
C(38)-C(30)-C(39)
C(40)-C(37)-C(41)
C(37)-C(40)-N(3)
85.0(1)
Cl(1)-Rh(1)-O(1)
86.3(2)
P(1)-Rh(1)-O(1)
C(23)-C(24)-O(2)
C(25)-C(30)-C(38)
C(31)-C(30)-C(39)
C(34)-C(37)-C(41)
C(30)-C(39)-N(2)
82.1(2)
122.3(9)
108.6(8)
107.1(8)
111.7(9)
176(1)
99.3(3)
118.5(6)
110.2(9)
106.3(9)
108(1)
P(1)-C(23)-C(24)
C(25)-C(30)-C(31)
C(31)-C(30)-C(38)
C(34)-C(37)-C(40)
C(30)-C(38)-N(1)
C(37)-C(41)-N(4)
113.3(7)
112.1(8)
112.4(9)
111(1)
177(1)
177(1)
179(1)
F igu r e 3. Perspective ORTEP view of the molecular
structure of 4a d with thermal ellipsoids drawn at 50%
probability.
F igu r e 4. Perspective ORTEP view of the molecular
structure of 5bc‚H2O with thermal ellipsoids drawn at 50%
probability. An H2O molecule was omitted for clarity.
groups adopt a staggered conformation. The three
angles around the Rh atom are 85.0° (Cl(1)-Rh(1)-
P(1)), 86.3° (Cl(1)-Rh(1)-O(1)), and 82.1° (P(1)-Rh(1)-
O(1)) and similar to those for 1a , due to no Cl‚‚‚H
interaction.
When complexes 1a and 1b were treated with mod-
elately electron withdrawing olefins such as fumaloni-
trile and dimethyl fumarate in methanol-CH2Cl2 at
room temperature or at reflux, the starting materials
were quantitatively formed. Similar treatment with
Me2-tcnq(e) failed to react.
((CN)2] proton of δ 6.50 appeared at δ ca. 0.2 lower field
than that for 3. The 31P{1H} NMR spectrum showed a
singlet at δ 15.9. The spectroscopic results suggested
that 5bc is a single insertion product arising from
insertion of tcne into the C-H bond adjacent to the
Ir-O bond. Indeed, X-ray crystal structure analysis
verified the structure (Figure 4 and Table 5). The crystal
contains a H2O molecule as a crystal solvent. The
molecule consists of two five-membered rings, Ir(1)-
P(1)O(3)C(19)C(20) and Ir(1)P(1)O(5)C(26)C(27), which
have a dihedral angle of 88.4(3)°. The O(3)‚‚‚O(5) was
separated by 2.83 Å. The CH(CN)2 and C(CN)2R groups
adopt a staggered conformation. The HC(CN)2C(CN)2
moiety is pointing in the same direction as the O(3)
atom, as found in the C(27)-C(28)-C(33)-C(34) torsion
angle of bond of -62(1)°. The Ir(1)-P(1) length of 2.272-
(4) Å is ca. 0.01 Å shorter than that for 2b , but the
Complex 2b bearing a (P,O,O′) tridentate ligand was
treated with 1 equiv of tcne at room temperature to give
reddish orange crystals, formulated as [Cp*Ir(TDMPP-
P,O,O′)(tcne)] 5bc by FAB mass spectrometry. The IR
spectrum showed a band at 2131 cm-1, due to a C-N
1
triple bond. The H NMR spectrum showed four singlet
resonances at δ 3.40, 3.45, 3.54, and 3.57, due to
methoxy groups, which are nonequivalent. The H[C-

270 Organometallics, Vol. 20, No. 2, 2001
Ta ble 5. Selected Bon d Len gth s (Å) a n d An gles (d eg) for 5bc‚H2O
Yamamoto et al.
Ir(1)-P(1)
2.272(4)
1.82(1)
1.81(2)
1.51(2)
1.09(2)
1.46(3)
1.16(2)
2.91
Ir(1)-O(3)
2.095(10)
1.37(2)
1.41(2)
1.56(2)
1.52(2)
1.14(2)
Ir(1)-O(5)
2.108(10)
1.36(2)
1.32(2)
1.52(2)
1.12(2)
1.43(2)
P(1)-C(19)
P(1)-C(26)
C(28)-C(33)
C(35)-N(1)
C(34)-C(37)
C(38)-N(4)
O(1)‚‚‚O(4)
O(4)‚‚‚O(6)
C(19)-C(20)
C(26)-C(27)
C(33)-C(34)
C(33)-C(36)
C(37)-N(3)
O(3)-C(20)
O(5)-C(27)
C(33)-(C35)
C(36)-N(2)
C(34)-C(38)
O(2)‚‚‚O(6)
3.15
O(3)‚‚‚O(5)
2.83
2.93
P(1)-Ir(1)-O(3)
82.3(3)
P(1)-Ir(1)-O(5)
81.2(3)
112(1)
103.2(5)
119.7(10)
110(1)
108(1)
114(1)
177(1)
O(3)-Ir(1)-O(5)
84.8(4)
123(1)
110(1)
102.1(6)
108(1)
106(1)
111(1)
171(2)
Ir(1)-P-C(19)
101.7(5)
118.1(8)
123(1)
113(1)
108(1)
111(1)
179(2)
176(2)
P(1)-C(19)-C(20)
Ir(1)-P(1)-C(26)
Ir(1)-O(5)-C(27)
C(28)-C(33)-C(35)
C(34)-C(33)-C(36)
C(33)-C(34)-C(38)
C(33)-C(36)-N(2)
C(19)-C(20)-O(3)
P(1)-C(26)-C(27)
C(19)-P(1)-C(26)
C(28)-C(33)-C(36)
C(35)-C(33)-C(36)
C(37)-C(34)-C(38)
C(34)-C(37)-N(3)
Ir(1)-O(3)-C(20)
C(26)-C(27)-O(5)
C(28)-C(33)-C(34)
C(34)-C(33)-C(35)
C(33)-C(34)-C(37)
C(33)-C(35)-N(1)
C(34)-C(38)-N(4)
Ta ble 6. Selected Bon d Len gth s (Å) a n d An gles (d eg) for 7bc‚0.5CH2Cl2
Ir(1)-P
2.277(2)
1.811(9)
1.814(9)
1.53(1)
1.12(1)
1.45(2)
1.12(2)
1.49(1)
1.14(1)
1.47(1)
1.18
Ir(1)-O(1)
2.095(6)
1.41(1)
1.42(1)
1.59(1)
1.47(2)
1.17(2)
1.52(1)
1.11(1)
1.47(1)
1.15(1)
1.10
Ir(1)-O(3)
2.097(6)
1.31(1)
1.31(1)
1.47(1)
1.14(1)
1.51(2)
1.60(1)
1.48(1)
1.13(1)
P(1)-C(101)
P(1)-C(201)
C(11)-C(103)
C(13)-N(1)
C(12)-C(15)
C(16)-N(4)
C(21)-C(23)
C(24)-N(6)
C(22)-C(26)
C(12)-H(1)
C(101)-C(102)
C(201)-C(202)
C(11)-C(12)
C(11)-C(14)
C(15)-N(3)
C(21)-C(203)
C(23)-N(5)
C(22)-C(25)
C(26)-N(8)
C(22)-H(2)
O(1)-C(102)
O(3)-C(202)
C(11)-C(13)
C(14)-N(2)
C(12)-C(16)
C(21)-C(22)
C(21)-C(24)
C(25)-N(7)
P(1)-Ir(1)-O(1)
82.7(2)
101.6(3)
119.5(6)
118.6(8)
106.2(8)
108.7(9)
112(1)
178(1)
178(1)
109.4(7)
109.6(8)
112.6(8)
175(1)
P(1)-Ir(1)-O(3)
79.9(2)
119.0(9)
103.6(3)
121.0(5)
111.7(9)
108.3(9)
112.4(9)
176(1)
106.2(8)
108.3(7)
109.8(7)
177(1)
O(1)-Ir(1)-O(3)
85.3(2)
123.2(9)
108.7(6)
99.9(4)
112.2(8)
109.6(9)
108.0(10)
178(1)
111.7(9)
106.3(7)
111.8(8)
179(1)
Ir(1)-P(1)-C(101)
Ir(1)-O(1)-C(102)
C(201)-C(202)-O(3)
C(103)-C(11)-C(12)
C(12)-C(11)-C(13)
C(11)-C(12)-C(15)
C(11)-C(13)-N(1)
C(12)-C(16)-N(4)
C(203)-C(21)-C(22)
C(23)-C(21)-C(24)
C(25)-C(22)-C(26)
C(22)-C(25)-N(7)
C(16)-C(12)-H(1)
P(1)-C(101)-C(102)
Ir(1)-P(1)-C(201)
Ir(1)-O(3)-C(202)
C(103)-C(11)-C(13)
C(12)-C(11)-C(14)
C(11)-C(12)-C(16)
C(11)-C(14)-N(2)
C(103)-C(11)-C(12)
C(22)-C(21)-C(33)
C(21)-C(22)-C(25)
C(21)-C(23)-N(5)
C(22)-C(26)-N(8)
C(25)-C(22)-H(2)
C(101)-C(102)-O(1)
P(1)-C(201)-C(202)
C(101)-P(1)-C(201)
C(103)-C(11)-C(14)
C(13)-C(11)-C(14)
C(15)-C(12)-C(16)
C(12)-C(15)-N(3)
C(103)-C(11)-C(13)
C(22)-C(23)-C(24)
C(21)-C(22)-C(66)
C(21)-C(24)-N(6)
C(15)-C(12)-H(1)
C(26)-C(22)-H(2)
175(1)
102.3
122.9
111.6
102.6
average Ir-O length is 0.03 Å longer than that for 2b.6
The Ir(1)-O(5) length is 0.01 Å longer than the Ir(1)-
O(3) one, relieving steric repulsion with the HC(CN)2C-
(CN)2 moiety. The angles around the Ir atom are not
different from those for 2b. The C(33)-C(34) bond
length of 1.56(2) Å is a conventional C-C single bond.
Complex 2b also reacted with 1 equiv of tcnq to form
the 1:1 adduct 6bd . The 1H NMR spectrum showed four
singlet resonances at δ 3.43, 3.44, 3.52, and 3.54 due to
methoxy groups and a singlet at δ 5.17 due to H[C(CN)2]
proton. The 31P{1H} NMR spectrum showed a singlet
at δ 18.3. Reaction of 2b with Me2-tcnq (e) gave the 1:1
adduct 6be based on FAB mass spectrometry, different
from the case of the reaction with 1b. The spectroscopic
data are in good agreement with the structure.
When 2b was treated with 2 equiv of tcne or tcnq,
the 1:2 adducts formulated as [Cp*IrCl(TDMPP-P,O,O′)-
(L)2] (7bc: L ) tcne; 8bd : L ) tcnq) were obtained. The
IR spectra showed bands at 2250 cm-1 for 7bc and at
F igu r e 5. Perspective ORTEP view of the molecular
structure of 7bc‚0.5CH2Cl2 with thermal ellipsoids drawn
at 50% probability. A CH2Cl2 molecule was omitted for
clarity.
1
2135 cm-1 for 8bd . The H NMR spectra showed two
singlets around δ 3.5 due to methoxy protons, suggest-
ing a symmetric structure. Indeed, X-ray structure
analysis of 7bc revealed that insertion of tcne occurred
at two C-H positions adjacent to the Ir-O bonds
(Figure 5). The H(2)C(22)(CN)2C(21)(CN)2 and H(1)-
C(12)(CN)2C(1)(CN)2 moieties are pointing in the same
direction, relieving steric repulsion between the two
groups. There are no significant differences in bond
lengths and angles between 5bc and 7bc.

Insertion of Cyanoolefins into C-H Bond
Organometallics, Vol. 20, No. 2, 2001 271
Sch em e 2. P ossible Rou te of F or m a tion of 8bd
mmol) at room temperature. After 4 h, the solvent was
removed and the solid was washed with diethyl ether. The
residue was crystallized from CH2Cl2 and diethyl ether to give
orange-brown crystals of 3a c (43.6 mg, 66.3%). IR (Nujol):
To examine a possible reaction path, the reaction of
5bc with tcne was carried out. Addition of tcne to an
orange solution of 5bc gave 7bc without a remarkable
change of color. This suggested that the reaction of 2b
with tcne proceeded through stepwise insertion.
1
2250 cm-1. UV/vis (CH2Cl2): λmax 392, 329 nm. H NMR (250
MHz, CDCl3): δ 1.50 (d, J PH ) 5.0 Hz, Cp*), 3.48 (s, OMe),
5.27 (s, CH2Cl2), 6.36 (s, CH), ca. 6.06 and 7.3-8.0 (c, ArH).
31P NMR (100 MHz, CDCl3): δ 45.2 (d, J RhP ) 142.7 Hz). FAB
mass: m/z: 709 [M]+, 673 [M - Cl]+. Anal. Calcd for
It has been observed that on addition of tcnq to a
solution of 2b, the mixture changed from yellow to pale
green, and finally became yellow-orange to form 6bd
or 8bd . This color change of the solution suggested the
formation of a charge-transfer complex. Attempts to
isolate a complex were unsuccessful. Thus, the solvent
was removed from the pale green solution. The IR
spectrum of the green residue showed two bands at 2180
and 2130 cm-1, which is lower in energy than that (2222
cm-1) for free tcnq and that (2209, 2180 cm-1) of
Li(tcnq). The electronic spectrum appeared at λmax 851
and 751 nm, in agreement with that of Li(tcnq). These
spectroscopic data are also in good agreement with those
of [Cp*Ir(MDMPP-P,O)][tcnq], with bands at 2191 and
2137 cm-1 in the IR spectrum and absorption bands at
C
35H31N4O2PClRh‚CH2Cl2: C, 54.46; H, 4.19; N, 7.06. Found:
C, 54.87; H, 4.08; N, 6.84.
Analogously, yellow crystals of iridium complex 3bc (42 mg,
43%) was obtained from 1b (80 mg, 0.121 mmol) and tcne (21.8
mg, 0.170 mmol) according to a precedure similar to 1a . UV/
vis (CH2Cl2): λmax 324 nm. 1H NMR (250 MHz, CDCl3): δ 1.53
(s, Cp*), 3.50 (s, OMe), 5.24 (s, CH2Cl2), 6.31 (s, HC(CN)2), ca.
6.13 and 7.2-7.9 (c, ArH). 31P NMR (100 MHz, CDCl3): δ 26.2
(s). FAB mass: m/z 798 [M]+. Anal. Calcd for C35H31N4O2PClIr‚
CH2Cl2: C, 48.96; H, 3.77; N, 6.34. Found: C, 49.24; H, 3.83;
N, 6.54.
Rea ction of 1a w ith tcn q. Orange crystals 4a d (28 mg,
32%) were obtained from 1a (60 mg, 0.103 mmol) and tcnq
(25 mg, 0.13 mol) by a procedure similar to 3a c. IR (Nujol):
λmax 853 and 768 nm in the electronic spectrum, derived
from the reaction of 1b with Li(tcnq). On the basis of
similarity of spectroscopic data, the green solid is
considered to be a weak charge-transfer intermediate,
[2b][tcnq] (Scheme 2).
1
2247 cm-1. UV/vis (CH2Cl2): λmax 398, 330 nm. H NMR (250
MHz, CDCl3): δ 1.35 (d, J PH ) 3.0 Hz, Cp*, 15H), 3.44 (s, OMe,
3H), 5.08 (s, CH, 1H), 7.51 (AB q, J ) 10.0 Hz, 4H), ca. 6.00
and 7.3-8.0 (c, ArH). 31P NMR (100 MHz, CDCl3): δ 48.4 (d,
J RhP ) 150.0 Hz). FAB mass: m/z 785 [M]+, 750 [M+ - Cl].
Anal. Calcd for C41H35N4O2PClRh: C, 62.73; H, 4.49; N, 7.14.
Found: C, 62.55; H, 4.55; N, 7.29.
These results suggest that the reaction with tcnq
consists of an initial formation of a charge-transfer
complex and proceeds with the electrophilic substitution
of tceq to the activated aromatic ring, leading to the
formal insertion of olefin. This reaction was accompa-
nied by stepwise insertion of olefin into the C-H bond.
However, since no green color species reminiscent of a
charge-transfer complex were observed in the reactions
with tcne, the reaction proceeds with the direct elec-
trophilic substitution to the aromatic ring of the (P,O)
bidentate or (P,O,O′) tridentate ligands.
Analogously, orange crystals of iridium complex 4bd (63%)
were obtained from 1b and tcnq according to a precedure
similar to 4a d . IR (Nujol): 2145 cm-1. UV/vis (CH2Cl2): λmax
1
398 nm. H NMR (250 MHz, CDCl3): δ 1.41 (s, Cp*), 3.45 (s,
OMe), 5.35 (s, CH2Cl2), 5.06 (s, HC(CN)2), ca. 6.0 and 7.2-7.9
(c, ArH). 31P NMR (100 MHz, CDCl3): δ 28.1 (s). FAB mass:
m/z 874 [M]+, 839 [M - Cl]+. Anal. Calcd for C41H35N4O2PClIr‚
0.25CH2Cl2: C, 55.32; H, 4.00; N, 6.26. Found: C, 55.36; H,
4.11; N, 6.02.
These reactions demonstrate the novel C-H bond
activation of aromatic rings in organometallic complexes
in connection with insertion reactions of strongly elec-
tron withdrawing cyanoolefins.
Rea ction of 2b w ith tcn e in a 1:1 Ra tio. To a solution of
2b (79.8 mg, 0.11 mmol) in CH2Cl2 (10 mL) was added tcne
(21.5 mg, 0.17 mmol) at room temperature. After stirring for
3 h, removal of the solvent and the crystallization of the
residue from CH2Cl2 and diethyl ether gave reddish orange
crystals of 5bc (40.1 mg, 42.3%). IR (Nujol): 2131 cm-1 1H
.
Exp er im en ta l Section
NMR (250 MHz, CDCl3): δ 1.54 (d, J PH ) 3.0 Hz, Cp*, 15H),
3.40 (s, OMe, 3H), 3.45 (s, OMe, 3H), 3.54 (s, OMe, 3H), 3.57
(s, OMe, 3H), 5.27 (s, CH2Cl2), 6.50 (s, CH), and 5.8-7.4 (c,
ArH, 8H). 31P NMR (100 MHz, CDCl3): δ 19.5 (s). FAB mass:
m/z: 867 [M]+, 832 [M - Cl]+. Anal. Calcd for C38H36N4O8PIr‚
0.5CH2Cl2: C, 50.79; H, 4.10; N, 6.15. Found: C, 50.72; H,
4.22; N, 6.19. Complex 6bd (71 mg, 68.4%) was obtained from
the reaction of 2b (80 mg, 0.11 mol) with tcnq (30 mg, 0.16
Gen er a l Meth od s. All complexes were prepared under
nitrogen atmosphere. Solvents were distilled under nitrogen
prior to use with diethyl ether distilled from LiAlH4 and
methylene chloride distilled from CaH2. Phosphines (MDMPP
and TDMPP)1b and their pentamethylcyclopentadienyl com-
plexes of rhodium5 and iridium6 were prepared according to
the literature. The infrared and electronic absorption spectra
were measured on FT/IR-5300 and U-best 30 spectrometers,
respectively. NMR spectrometry was carried out on a Bruker
AC250. 1H NMR spectra were measured at 250 MHz, and 31P-
{1H} NMR spectra were measured at 100 MHz using 85% H3-
PO4 as an external reference.
mmol) by a procedure similar to 5bc. IR (Nujol): 2131 cm-1
.
1H NMR (250 MHz, CDCl3): δ 1.44 (d, J PH ) 1.8 Hz, Cp*, 15H),
3.43 (s, OMe, 3H), 3.44 (s, OMe, 3H), 3.52 (s, OMe, 3H), 3.55
(s, OMe, 3H), 5.17 (s, CH), and 6.0-8.0 (c, ArH, 9H). 31P NMR
(100 MHz, CDCl3): δ 18.3 (s). Anal. Calcd for C44H40N4O6PIr:
C, 55.98; H, 4.27; N, 5.94. Found: C, 55.77; H, 4.22; N, 6.11.
Complex 6be (53%) was obtained by the reaction between 2b
Rea ction of 1a w ith tcn e. To a solution of 1a (53.2 mg,
0.092 mmol) in CH2Cl2 (10 mL) was added tcne (13 mg, 0.010

272 Organometallics, Vol. 20, No. 2, 2001
Yamamoto et al.
1
and Me2-tcnq (e). IR(Nujol): 2247 cm-1. H NMR (250 MHz,
hexane or CH2Cl2/ether. Cell constants were determined from
20-25 reflections on a Rigaku AFC5S four-circle automated
diffractometer. The crystal parameters along with data col-
lections are summarized in Table 1. Data collection was carried
out by a Rigaku AFC5S refractometer at 27 °C except a AFC7R
diffractometer at -118 °C was used for 7bc‚0.5CH2Cl2. Inten-
sities were measured by the 2θ-ω scan method using Mo KR
radiation (λ ) 0.71069 Å). Throughout the data collection the
intensities of the three standard reflections were measured
every 150 or 200 reflections as a check of the stability of the
crystals, and no decay was observed. Intensities were corrected
for Lorentz and polarization effects. The absorption correction
was made. Atomic scattering factors were taken from Cromer
CDCl3): δ 1.42 (d, J PH ) 1.8 Hz, Cp*, 15H), 2.36 (s, Me, 3H),
2.43 (s, Me, 3H), 3.44 (s, OMe, 3H), 3.48 (s, OMe, 3H), 3.56 (s,
OMe, 3H), 3.57 (s, OMe, 3H), 5.03 (s, CH, 1H), 5.27 (s, CH2-
Cl2) and 5.7-7.5 (c, ArH, 10H). 31P NMR (100 MHz, CDCl3):
δ 17.5 (s). FAB mass: m/z 867 [M]+, 832 [M - Cl]+. Anal. Calcd
for C46H44N4O8PIr‚0.5CH2Cl2: C, 55.05; H, 4.56; N, 5.76.
Found: C, 54.49; H, 4.52; N, 5.78.
Rea ction of 2b w ith tcn e in a 1:2 Ra tio. To a solution of
2b (79.8 mg, 0.11 mmol) in CH2Cl2 (10 mL) was added tcne
(40.7 mg, 0.32 mmol) at room temperature. After stirring for
3 h, the solvent was removed and the residue was crystallized
from CH2Cl2 and diethyl ether to give dark green crystals of
7bc (42 mg, 44.8%). IR (Nujol): 2135 cm-1. 1H NMR (250 MHz,
CDCl3): δ 1.59 (d, J PH ) 1.8 Hz, Cp*, 15H), 3.47 (s, OMe, 6H),
3.60 (s, OMe, 6H), 5.27 (s, CH2Cl2), 6.28 (s, CH, 1H), and 6.0-
8.0 (c, ArH, 9H). 31P NMR (100 MHz, CDCl3): δ 19.7 (s). FAB
mass: m/z 996 [M + 1]+, 929 [M - HC(CN)2]+, 865 [M - H2-
TCNE]+. Anal. Calcd for C44H36N8O6PIr‚0.5CH2Cl2: C, 51.46;
H, 3.59; N, 10.76. Found: C, 51.77; H, 3.74; N, 10.90.
Rea ction of 2b w ith tcn q in a 1:2 Ra tio. To a solution of
2b (80 mg, 0.11 mmol) in CH2Cl2 (10 mL) was added tcnq (52
mg, 0.27 mmol) at room temperature. After stirring for 3 h,
the solvent was removed and the residue was crystallized from
CH2Cl2 and diethyl ether to give orange crystals of 8bd (85.3
and Waber with the usual tabulation.12 Anomalous dispersion
16
effects were included in Fcalc
; the values of ∆f ′ and ∆f′′ were
those of Creagh and McAuley.13 All calculations were per-
formed using the teXsan crytallographic software package.14
Deter m in a tion of th e Str u ctu r es. The structures except
7bc‚0.5CH2Cl2, which was solved by direct methods, were
solved by Patterson methods (DIRDIF92, PATTY).
The positions of all non-hydrogen atoms except the non-
hydrogen atoms of a CH2Cl2 crystal solvent in 3a c‚CH2Cl2 were
refined with anisotropic thermal parameters by using full-
matrix least-squares methods. All hydrogen atoms of other
complexes except hydrogen atoms H1 and H2 of 7bc‚0.5CH2-
Cl2, which were determined by difference Fourier syntheses,
were calculated at the ideal positions with the C-H distance
of 0.95 Å. Final difference Fourier syntheses showed peaks at
mg, 67.5%). IR (Nujol): 2250 cm-1 1H NMR (250 MHz,
.
CDCl3): δ 1.41 (d, J PH ) 1.8 Hz, Cp*, 15H), 3.42 (s, OMe, 6H),
3.55 (s, OMe, 6H), 5.15 (s, CH), 5.27 (s, CH2Cl2) and 6.0-8.0
(c, ArH, 7H). 31P NMR (100 MHz, CDCl3): δ 18.7 (s). FAB
mass: m/z 1148 [M]+. Anal. Calcd for C56H44N8O6PIr‚0.5CH2-
Cl2: C, 56.99; H, 3.81; N, 9.41. Found: C, 56.53; H, 3.91; N,
8.70.
Rea ction of 6bd w ith tcn q. To a solution of 6bd (45 mg,
0.048 mol) in CH2Cl2 (10 mL) was added tcnq (mg, mol) at
room temperature, and the mixture was stirred for 3 h. The
solvent was removed and the residue was crystallized from
CH2Cl2 and diethyl ether to form orange crystals of 8bd (35
mg, 64%).
Rea ction of 1b w ith Li[tcn q]. To a solution of 1b (40 mg,
0.06 mmol) in CH2Cl2 (10 mL) was added Li[tcnq] (15 mg, 0.07
mmol) at room temperature. After 3 h, the mixture was
filtered, the solvent was concentrated from the filtrate, and
the residue was crystallized from CH2Cl2 and diethyl ether to
give pale green complex [Cp*Ir(MDMPP-P,O)(tcnq)] (34 mg,
67.5%). IR (Nujol): 2191, 2137 cm-1. UV-vis (CH2Cl2): 853,
768 nm. 1H NMR (250 MHz, CDCl3): δ 1.57 (bs, Cp*, 15H),
3.39 (bs, OMe, 3H), 4.27 (s, CH2Cl2), and 6.0-8.0 (c, ArH, 17H).
31P NMR (100 MHz, CDCl3): δ 69.4 (s). FAB mass: m/z 635
[[Cp*Ir(MDMPP-P,O)] + 1]+. Anal. Calcd for C41H35N4O2PIr‚
CH2Cl2: C, 54.60; H, 4.04; N, 6.06. Found: C, 54.89; H, 4.20;
N, 6.08.
heights up to 0.41-0.61 e A-3
.
Ack n ow led gm en t. We thank Professor Shigetoshi
Takahashi and Dr Fumie Takei of The Institute of
Scientific and Industrial Research, Osaka University,
for measurements of FAB mass spectrometry.
Su p p or tin g In for m a tion Ava ila ble: Tables of atomic
coordinates and equivalent isotropic parameters, hydrogen
coordinates, and isotropic displacement parameters for 3a c‚
CH2Cl2, 3bc, 4a d , 5bc‚H2O, and 7bc‚0.5CH2Cl2. The CCDC
numbers of 3bc and 4a d are 103207 and 103208, respectively.
This material is available free of charge via the Internet at
http://pubs.acs.org.
OM000781C
(12) Cromer, D. T.; Waber, J . T. International Tables for X-ray
Crystallography, Vol. IV; The Kynoch Press: Birmingham, England,
1974; Table 2.2A.
(13) Ibers, J . A.; Hamilton, W. C. Acta Crystallogr. 1964, 17, 781.
(14) Creagh, D. C.; McAuley, W. J . In International Tables for
Crystallography, Vol. C; Wilson, A. J . C., Ed.; Kluwer Academic
Publishers: Boston, 1992; Table 4.2.6.8, pp 219-222 .
(15) teXsan, Crystal Structure Analysis Package; Molecular Struc-
ture Corporation: 1985 & 1992.
Da ta Collection . Complexes 3a c‚CH2Cl2, 3bc, 4a d , 5bc‚
H2O, and 7bc‚0.5CH2Cl2 were recrystallized from CH2Cl2/