Synthesis and characterization of bis(triphenylphosphine)(ketone)copper and bis(triphenylphosphine)bis(ketone)copper complexes; Crystal structure of bis(triphenylphosphine)bis(phenalenone)copper tetrafluoroborate

Article abstract of DOI:10.1016/S0020-1693(96)05411-4

The bis(triphenylphosphine)copper complexes of phenalenone (6), diphenylcyclopropenone (7), tropone (8), bis(phenalenone) (9), bis(diphenylcyclopropenone) (10) and bis(tropone) (11) were prepared by treating bis(triphenylphosphine)copper tetrafluoroborate

Full text of DOI:10.1016/S0020-1693(96)05411-4

Inorganica Chimica Acta 256 (1997) 35–40
Synthesis and characterization of
bis(triphenylphosphine)(ketone)copper and
bis(triphenylphosphine)bis(ketone)copper complexes; crystal structure
of bis(triphenylphosphine)bis(phenalenone)copper tetrafluoroborate
U
U
See Lin a, , Ching-Jane Lin a, Shin-Tran Cheng a, Yuh-Sheng Wen b, Ling-Kang Liu b,
a Department of Chemistry, National Changhua University of Education, Changhua, Taiwan 50058, ROC
b Institute of Chemistry, Academia Sinica, Taipei, Taiwan 11529, ROC
Received 14 February 1996; revised 10 June 1996
Abstract
The bis(triphenylphosphine)copper complexes of phenalenone (6), diphenylcyclopropenone (7), tropone (8), bis(phenalenone) (9),
bis(diphenylcyclopropenone) (10) and bis(tropone) (11) were prepared by treating bis(triphenylphosphine)copper tetrafluoroborate (5)
with the respective basic ketones phenalenone (2), diphenylcyclopropenone (3), or tropone (4) in one and two equivalent amounts. The
crystal structure of the bis(phenalenone) complex (9), (Ph3P)2(phenalenone)2CuqBF4yP0.5phenalenone, was determined in order to
confirm the copper to oxygen s-bonds. The results also indicate that there is no significant change in the alternation of C–C bond-type in the
phenalenone ring upon coordination and that there is a p–p interaction between the coordinated phenalenone and the phenalenone solvate in
˚
the solid state. Complex 9 crystallizes in the triclinic space group P-1, with as10.898(1), bs13.522(2), cs19.597(3) A, as76.32(1),
3
˚
bs78.62(1), gs83.65(1)8, Zs2, Vs2744.6(6) A , Rs0.058, Rws0.064 for 4777 reflections.
Keywords: Crystal structures; Copper complexes; Ketone complexes
1. Introduction
Transition metal complexes of ketones in the form of sim-
ple adducts such as FeCl3POCPh2 and MgBr2POCPh2 have
been known for over eighty years [1], the ketonic oxygen
being presumed to be s-bonded to the metal ions [2]. About
two decades ago, an interest in complexes of the carbonyl
function with an organotransition-metal group developed. In
1971, Silverthorn reported a novel iron ketone complex (h5-
C5H5)Fe(dppe)(OCMe2)( 1a) where dppesPh2PCH2-
CH2PPh2 [3]. Complex 1a is not stable in air or moisture,
Scheme 1.
and could not be isolated. Later, Rosenblum and co-workers
prepared various Fp(carbonyl) complexes derived from sim-
the contributions of resonance forms 29, 39 and 49, shown in
ple and conjugated ketones, aldehydes, esters and amides
where Fps(h5-C5H5)Fe(CO)2 [4]. In 1982, Boudjouk
Scheme 2 [6]. The resonance forms 29, 39 and 49 apparently
play an important role during the reactions, favoring the rapid
formation of stable oxygen–metal bonds. Gladysz and co-
workers conducted extensive studies on Re complexes of
et al. also prepared complexes of Fp(carbonyl), 1b–1d,as
outlined in Scheme 1 [5].
Phenalenone (2), diphenylcyclopropenone (3) and tro-
organic aldehydes and ketones and found that thecoordinated
carbonyl groups are activated toward nucleophilicattack[7].
With a significant role in metal-promoted transformations
of organic substrates by CuI, the CuI–OR unit is usually
pone (4) are typical basic ketones. The highly polar nature
of the carbon–oxygen bond is due to a significant degree to
U Corresponding authors.
0020-1693/97/$17.00 q 1997 Elsevier Science S.A. All rights reserved
PII S0020-1693(96)05411-4

36
S. Lin et al. / Inorganica Chimica Acta 256 (1997) 35–40
1H NMR (CDCl3): d 8.62 (d, 1H, Js7.2 Hz), 8.22 (d, 1H,
Js8.3 Hz), 8.05 (d, 1H, Js8.4 Hz), 7.79–7.62 (m, 4H),
7.39–7.24 (m, 30H), 6.73 (d, 1H, Js8.8 Hz). IR (CH2Cl2):
1643 cmy1 (n(CO)). UV (CH2Cl2, nm (log e)): 228
(4.11), 246 (4.05), 314 (2.91), 358 (3.40), 384 (3.34).
Anal. Calc. for C49H38CuOP2BF4PH2O: C, 67.40; H, 4.59.
Found: C, 67.41; H, 4.57%.
2.3. Preparation of bis(triphenylphosphine)-
(diphenylcyclopropenone)copper tetrafluoroborate (7)
Scheme 2.
This was prepared by a method similar to that described
above by using (Ph3P)2CuCl (0.768 g, 1.23 mmol), AgBF4
(0.240 g, 1.23 mmol), CH2Cl2 (30 ml) and diphenylcyclo-
propenone (3) (0.268 g, 1.30 mmol). The resulting solution
was stirred for 50 min at room temperature. The product was
obtained as a light yellow solid (0.78 g, 72%); m.p. 114–
synthesized in situ because of its high reactivity and relative
instability [8]. As the above basic ketones 2–4 have a built-
in high polarity resembling an alkoxide in the molecule, the
CuI–OR unit may likely be constructed using these neutral
ketones. In a hope to reveal more fundamental information,
we have recently extended the same approach to the synthesis
of (Ph3P)2Cu(ketone)nBF4 complexes(ns1, 2) asreported
herein.
1
1188C (dec.). H NMR (CDCl3): d 8.00–7.76 (m, 6H),
7.42–7.22 (m, 30H), 7.01 (d, 4H, Js8.2 Hz). IR (CH2Cl2):
1627 cmy1 (n(CO)). UV (CH2Cl2, nm (log e)): 228
(4.13). Anal. Calc. for C51H40CuOP2BF4PH2O: C, 68.12; H,
4.67. Found: C, 68.07; H, 4.69%.
2. Experimental
2.4. Preparation of bis(triphenylphosphine)(tropone)-
copper tetrafluoroborate (8)
2.1. General
All solvents were routinelypurifiedbystandardprocedures
and stored under nitrogen [9]. All reactions were carried out
in dry solvents under oxygen-free nitrogen. Commercial rea-
gents including diphenylcyclopropenone, PPh3, CuCl and
AgBF4 (Aldrich Co.) were used without further purification.
Phenalenone [10], tropone [11] and (Ph3P)2CuCl [12]
were prepared following the published methods. IR spectra
were recorded on aJascoFT/IR300Espectrometer.1HNMR
spectra were registered on a Bruker AC 400 NMR spectrom-
eter. UV spectra were measured on a Perkin-Elmer Lambda
5 spectrometer. Elemental analyses were done at the Analysis
Center of National Cheng-Kung University.
This was prepared by a method similar to that described
above by using (Ph3P)2CuCl (0.521 g, 0.835 mmol), AgBF4
(0.163 g, 0.835 mmol), CH2Cl2 (30 ml) and tropone (4)
(0.09 g, 0.850 mmol). The resulting solution was stirred for
30 min at room temperature. The product was obtained as a
dark golden solid (0.62 g, 70%); m.p. 104–1088C. 1H NMR
(CDCl3): d 7.73–7.48 (m, 4H), 7.37–7.18 (m, 30H), 7.02
(d, 2H, Js12 Hz). IR (CH2Cl2): 1558 cmy1 (n(CO)). UV
(CH2Cl2, nm (log e)): 230 (4.23). Anal. Calc. for
C43H36CuOP2BF4: C, 66.13; H, 4.61. Found: C, 66.20; H,
4.61%.
2.2. Preparation of bis(triphenylphosphine)-
(phenalenone)copper tetrafluoroborate (6)
2.5. Preparation of bis(triphenylphosphine)-
bis(phenalenone)copper tetrafluoroborate (9)
A 100 ml Schlenk flask that had been oven dried and
purged with nitrogen was charged with (Ph3P)2CuCl (0.695
g, 1.12 mmol), AgBF4 (0.217 g, 1.12 mmol) and CH2Cl2
(30 ml), and stirred for 30 min at room temperature. The
reaction mixture was then filtered under nitrogen using afilter
funnel and filter aid (Celite) into a three-neck 100 ml round-
bottomed flask. To this solution was added phenalenone (2)
(0.216 g, 1.20 mmol), and the resulting solution was stirred
at 408C for 30 min. After being cooled to room temperature,
the reaction mixture was filtered and n-hexane added to the
filtrate to precipitate a red solid. The solid was collected and
washed with ether until the washings were colorless, giving
analytically pure 6 (0.73 g, 78%); m.p. 133–1388C (dec.).
This was prepared by a method similar to the preparation
of 6 but with 2 equiv. of 2: (Ph3P)2CuCl (0.600 g, 0.963
mmol), AgBF4 (0.188 g, 0.963 mmol), CH2Cl2 (30 ml) and
2 (0.35 g, 1.94 mmol). The resulting solution was stirred for
30 min at 408C. The product was obtained as deep red solid
(0.785 g, 76%); m.p. 139–1448C. 1H NMR (CDCl3): d 8.58
(d, 2H, Js7.4 Hz), 8.22 (d, 2H, Js6.8 Hz), 8.03 (d, 2H,
Js8.2 Hz), 7.80–7.73 (m, 6H), 7.36–7.21 (m, 30H), 6.68
(d, 2H, Js9.8 Hz). IR (CH2Cl2): 1643 cmy1 (n(CO)).
UV (CH2Cl2, nm (log e)): 232 (4.10), 248 (4.17), 358
(3.53), 380 (3.46). Anal. Calc. for C62H46CuO2P2BF4:C,
71.93; H, 4.45. Found: C, 71.77; H, 4.50%.

S. Lin et al. / Inorganica Chimica Acta 256 (1997) 35–40
37
Table 1
2.6. Preparation of bis(triphenylphosphine)-
Crystallographic data and refinement details for complex 9
bis(diphenylcyclopropenone)copper tetrafluoroborate (10)
Crystal system
Space group
triclinic
P-1
10.898(1)
13.522(2)
19.597(3)
76.32(1)
78.62(1)
83.65(1)
2744.6(6)
C68.5H50BCuF4O2.5P2
1125.45
deep red
0.30=0.25=0.31
2
298
This was prepared by a method similar to the preparation
of 7 with 2 equiv. of 3: (Ph3P)2CuCl (0.478 g, 0.767 mmol),
AgBF4 (0.149 g, 0.767 mmol), CH2Cl2 (30 ml) and 3 (0.32
g, 1.55 mmol). The resulting solution was stirred for 60 min
at room temperature. The product was obtained as a light
yellow solid (0.62 g, 76%); m.p. 77–818C (dec.). 1H NMR
(CDCl3): d 8.27 (d, 2H, Js7.8 Hz), 7.97–7.59 (m, 8H),
7.55–7.01(m, 40H). IR (CH2Cl2 ): 1626 cmy1 (n(CO)).
UV (CH2Cl2, nm (log e)): 358 (3.56). Anal. Calc. for
C66H50CuO2P2BF4: C, 72.91; H, 4.61. Found: C, 72.76; H,
4.83%.
˚
a (A)
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
3
˚
V (A )
Empirical formula
Molar mass (g)
Crystal color
Crystal size (mm)
Z
T (K)
F(000)
1162
1.362
0.71069 (Mo Ka)
0.49
calc (Mg my3
)
2.7. Preparation of bis(triphenylphosphine)bis(tropone)-
copper tetrafluoroborate (11)
D
l (A)
˚
m (mmy1
)
Scan mode
2umax (8)
h, k, l range
No. unique reflections
No. reflections with Io)2.5s(Io)
No. atoms
u/2u
44.9
This was prepared by a method similar to the preparation
of 8 with 2 equiv. of 4: (Ph3P)2CuCl (0.476 g, 0.765 mmol),
AgBF4 (0.149 g, 0.765 mmol), CH2Cl2 (30 ml) and4(0.165
g, 1.55 mmol). The resulting solution was stirred for 45 min
at room temperature. The product was obtained as a dark
green solid (0.45 g, 68%); m.p. 118–1238C (dec.). 1H NMR
(CDCl3): d 8.23–8.20 (m, 2H), 7.55–7.01 (m, 40H). IR
(CH2Cl2): 1582 cmy1 (n(CO)). UV(CH2Cl2, nm(loge)):
248 (3.14). Anal. Calc. for C50H42CuO2P2BF4: C, 67.69; H,
4.74. Found: C, 67.22; H, 4.71%.
y11,11; 0,14; y20,21
7168
4777
135
No. parameters
746
R a
0.058
0.064
2.52
0.159
0.82
b
Rw
GOF c
Max. D/s
Max. difference peak (e A
y3
˚
)
a Rs8NFoyFcN/8NFoN.
b Rws[8w(FoyFc)2/8(wFo2)]1/2
.
2.8. X-ray crystallographic analysis for complex 9
c GOFs[8w(FoyFc)2/(no. of reflectionsyno. of parameters)]1/2
.
Dark red crystals of complex 9 suitable for X-ray crystal-
lographic study were prepared by diffusion of n-hexane into
a concentrated CH2Cl2 solution of complex 9 under nitrogen
at 48C. The single crystal X-ray diffraction measurements
were performed on a Nonius CAD-4 automated diffracto-
meter using graphite monochromated Mo Ka radiation. 25
high-angle reflections (14.99-2u-32.268) were used in a
least-squares fit to obtain accurate cell constants. The triclinic
space group P-1 was assigned on the basis of the systematic
absences. Diffraction intensitieswerecollectedupto2u-458
using u/2u scan technique. The reflectionswithIo)2.5s(Io)
were judged as observations and used for solution and struc-
ture refinement. DatawerecorrectedforLorentz–polarization
factors. An empirical absorption correction based on a series
of C scans was applied to the data. The structure was solved
by direct methods [13], and refined by a full-matrix least-
squares routine [14] with anisotropic thermal parametersfor
all non-hydrogen atoms. All of the hydrogen atoms were
placed isotropically at their calculated positions(C–Hs1.00
3. Results and discussion
3.1. Preparation
The preparation of tertiary phosphine complexes of copper
and silver of the type LnMX (Lstertiary phosphine; ns
1–4; Xscoordinating or non-coordinating anion) following
the methods of Mann et al. [15] generally involves the
reaction of stoichiometric amounts of phosphine ligand
with appropriate copper or silver halides. The treatment
y
of (Ph3P)2CuqBF4 (5), readily obtained by mixing
(Ph3P)2CuCl and AgBF4 in a CH2Cl2 solution, with ketones
2, 3 and 4 in one and two equivalent amounts furnished
the (Ph3P)2Cu(ketone)qBF4y2 and (Ph3P)2Cu(ketone)
-
q
y
BF4 complexes 6–11 in excellent quality and yields. The
preparation is presented in Scheme 3.
Being somewhat hygroscopic, both the (Ph3P)2Cu-
(ketone)qBF4y2 complexes 6–8 and(Ph3P)2Cu(ketone)
-
q
˚
A) and fixed in the calculations. For a summary of crystal
BF4y complexes 9–11 could be handled in air. They are very
soluble in common organic solvents such as CHCl3 and
CH2Cl2. Previously, numerous simple metal halide adducts
of 2 [16], 3 [17] and 4 [18] have been prepared and char-
acterized withaverylowsolubility. Apparently,thesolubility
data and refinement details, see Table 1. Selected bond dis-
tances and angles are listed in the caption of Fig. 1. The final
atomic fractional coordinates of the non-H atoms are listed
in Table 2.

38
S. Lin et al. / Inorganica Chimica Acta 256 (1997) 35–40
Table 2
Table 2 (continued)
Final atomic fractional coordinates for non-H atoms of compound 9
Atom
x
y
z
Biso
4.4(3)
Atom
x
y
z
Biso
3.84(4)
C86
C91
C92
C93
C94
C95
C96
C101
C102
C103
C104
C105
C106
C107
C108
C109
C110
B
0.3155(6)
0.5516(5)
0.5818(6)
0.5884(6)
0.5681(6)
0.5426(6)
0.5335(5)
0.1222(10)
0.2108(14)
0.2159(8)
0.0907(5)
0.2187(4)
0.1820(4)
0.2503(5)
0.3530(5)
0.3900(4)
0.3221(4)
0.6529(7)
0.5805(12)
0.4797(8)
0.6659(6)
0.7113(16)
0.6123(11)
0.6001(11)
0.5000
0.4315(12)
0.5446(11)
0.6947(6)
0.7481(6)
0.6575(4)
0.7542(6)
0.6221(5)
0.4347(3)
0.3842(3)
0.4518(3)
0.4939(3)
0.4681(3)
0.4006(3)
0.3583(3)
0.4512(5)
0.4294(8)
0.4403(4)
0.5170(5)
0.4890(9)
0.5492(8)
0.4888(7)
0.5000
0.4758(8)
0.4641(7)
0.2975(4)
0.2541(4)
0.3577(3)
0.3083(5)
0.2671(3)
Cu
0.52100(7)
0.50908(15)
0.53150(15)
0.6427(4)
0.3477(4)
0.0804(13)
0.7549(7)
0.8336(7)
0.9509(8)
1.1266(10)
1.1919(9)
1.1430(7)
0.9609(10)
0.8307(8)
0.7576(7)
0.8276(8)
0.9507(5)
1.0209(8)
1.0105(10)
0.2751(6)
0.3239(8)
0.2574(7)
0.0582(9)
y0.0789(8)
y0.1315(8)
y0.1009(8)
y0.0194(8)
0.1040(8)
0.1498(7)
0.0761(5)
0.1203(9)
y0.0476(8)
0.3750(5)
0.3863(6)
0.2787(7)
0.1621(7)
0.1510(6)
0.2561(6)
0.6451(5)
0.6885(6)
0.7943(6)
0.8601(6)
0.8180(6)
0.7116(6)
0.4914(5)
0.5372(6)
0.5300(6)
0.4763(6)
0.4287(6)
0.4366(6)
0.6575(5)
0.7798(6)
0.8812(6)
0.8624(6)
0.7444(6)
0.6420(6)
0.3881(5)
0.3477(6)
0.2386(6)
0.1666(6)
0.2048(6)
0.20697(5)
0.13034(12)
0.13312(11)
0.3282(3)
0.2927(4)
0.7402(10)
0.3397(6)
0.2494(5)
0.2482(6)
0.3441(10)
0.4367(10)
0.5180(7)
0.5924(7)
0.5776(8)
0.4982(5)
0.4135(8)
0.4222(5)
0.3471(7)
0.5122(6)
0.3572(5)
0.4657(7)
0.5473(7)
0.6221(6)
0.6078(6)
0.5189(6)
0.3465(8)
0.2526(7)
0.2582(5)
0.3548(6)
0.4457(4)
0.5403(5)
0.4274(6)
0.0525(4)
y0.0516(5)
y0.1065(5)
y0.0582(6)
0.0451(6)
0.1007(5)
0.0445(4)
y0.0236(5)
y0.0879(5)
y0.0838(5)
y0.0166(5)
0.0481(5)
0.2145(4)
0.3099(5)
0.3742(5)
0.3436(5)
0.2496(5)
0.1843(4)
0.0343(4)
0.0648(5)
0.21420(4)
0.12648(8)
0.32831(8)
0.1828(2)
0.2260(3)
0.4501(8)
0.1566(4)
0.1220(4)
0.0860(5)
0.0466(5)
0.0411(5)
0.0658(4)
0.1286(5)
0.1674(5)
0.1795(4)
0.1463(4)
0.1106(3)
0.0797(4)
0.1065(4)
0.2447(3)
0.2270(4)
0.2398(4)
0.2849(4)
0.3217(4)
0.3418(4)
0.3503(5)
0.3383(5)
0.3032(4)
0.2792(4)
0.2920(3)
0.2734(4)
0.3274(4)
0.1462(3)
0.1535(3)
0.1714(4)
0.1809(4)
0.1744(4)
0.1572(3)
0.1054(3)
0.1612(3)
0.1495(4)
0.0815(4)
0.0257(3)
0.0370(3)
0.0409(3)
0.0241(3)
3.4(3)
4.2(3)
5.0(3)
5.0(3)
4.8(3)
3.8(3)
11.0(7)
7.3(9)
9.8(6)
9.9(6)
11.4(14)
6.9(9)
6.9(9)
4.7(5)
8.1(11)
6.4(8)
6.7(6)
19.6(6)
14.4(5)
22.8(8)
13.2(4)
P1
P2
O1
O2
O3
C1
C2
C3
C4
C5
C6
C7
C8
C9
3.61(8)
3.29(7)
6.0(3)
7.2(3)
12.2(10)
8.0(5)
7.2(5)
9.0(6)
14.7(8)
13.7(9)
9.1(6)
10.1(6)
9.7(6)
6.6(4)
10.5(6)
4.8(3)
8.3(5)
9.8(6)
5.5(4)
8.5(5)
7.8(5)
9.2(6)
9.2(6)
8.6(5)
9.6(6)
10.1(7)
7.1(5)
7.1(4)
4.2(3)
8.3(5)
7.9(5)
3.7(3)
5.1(4)
6.8(4)
6.7(4)
6.6(4)
5.4(3)
3.5(3)
4.8(3)
5.6(4)
6.0(4)
5.9(4)
4.6(3)
3.6(3)
4.8(3)
5.7(4)
5.4(4)
5.0(4)
4.3(3)
3.3(3)
4.9(3)
5.7(4)
5.9(4)
5.4(4)
4.3(3)
3.3(3)
4.2(3)
5.1(4)
5.7(4)
5.5(4)
y0.1048(10)
y0.0084(19)
y0.2094(15)
0.0008(15)
0.0000
0.0979(16)
0.1227(14)
0.5295(10)
0.6142(8)
0.5656(7)
0.4364(8)
0.5174(6)
C10
C11
C12
C13
C21
C22
C23
C24
C25
C26
C27
C28
C29
C30
C31
C32
C33
C41
C42
C43
C44
C45
C46
C51
C52
C53
C54
C55
C56
C61
C62
C63
C64
C65
C66
C71
C72
C73
C74
C75
C76
C81
C82
C83
C84
C85
Fl
F2
F3
F4
Scheme 3.
of the adducts varies individually and depends on the organo-
metallic moiety. For example, (CO)5Mn(phenalenone)-
BF4 [19] virtually does not dissolve in CH2Cl2, and
Fp(phenalenone)BF4 [5] slightly dissolves in CH2Cl2.
Complexes 6–11 do not show significant wavelengthshifts
relative to the free ketones, both in the UV spectra and in the
IR spectra. The reported ketone adducts, e.g. MXn(ketone),
Fp(ketone)BF4 and (CO)5Mn(ketone)BF4, however,
exhibit to various degrees bathochromic shifts in the UV
spectra. Complexes Fp(phenalenone)BF4 and (CO)5Re-
(phenalenone)BF4 [19] also reveal a considerable Dn(CO)
of 151 and 158 cmy1 in the IR spectra. A high dependence
on the attached organometallic moieties is apparent.
y0.0420(4)
y0.0905(3)
y0.0737(3)
y0.0087(3)
0.3419(3)
0.3182(3)
0.3238(4)
0.3522(4)
0.3750(4)
0.3698(3)
0.3725(3)
0.3409(3)
0.3707(3)
0.4321(4)
0.4638(3)
y0.0051(5)
y0.1053(5)
y0.1381(5)
y0.0675(4)
0.0703(4)
3.2. Structure
0.0012(4)
The ORTEP diagram of complex 9 is given in Fig. 1. The
molecular features confirm that the Cu atom is indeed s-
bonded to two phenalenone O atoms. Selected bonddistances
and angles are listed in the caption of Fig. 1. The crystal
y0.0469(5)
y0.0249(5)
0.0439(5)
(continued)

S. Lin et al. / Inorganica Chimica Acta 256 (1997) 35–40
39
˚
1.278(5) A from the Cu–P1–P2 plane whereas O2 is at
˚
y1.860(5) A from the same plane, the O2 displacement
˚
being 0.582 A larger. The angles of Cu involving O2 are
relatively smaller than those involving O1. The torsion angle
of Cu–O1–C1–C2, 14.3(3)8, is very different from that of
Cu–O2–C21–C22, 48.9(5)8, i.e. the Cu–O2 bond is twisted
away more from coplanarity with the attached phenalenone
than the Cu–O1 bond. The O1–phenalenone is characterized
with alternatively single and double bonds for the 12 peri-
metric carbon atoms C1 to C12, whereas in the O2–phena-
lenone the fragment of C21–C30–C29–C28 is delocalized.
The ketonic O angles are 137.2(5)8 for /Cu–O1–C1 and
156.1(5)8 for /Cu–O2–C21, suggesting that the ketonic O1
is more sp2-like in bonding and O2 probably more sp-like.
At least, it is an indication that O2 is in a much more crowded
environment. In the literature, the X-ray structure of 9-butox-
yphenalenone has been found to show a perimetric bond type
similar to that of the O2–phenalenone skeleton [20]. The X-
ray structure of free phenalenone itself has not yet been
reported.
Fig. 1. An ORTEP molecular plot of complex
9 including the
(Ph3P)2Cu(phenalenone)2q4 cation, BF y anion and one phenalenone sol-
˚
vate molecule, with the numbering sequence. Selected bond distances (A):
Cu–P(1) 2.2374(17), Cu–P(2) 2.2430(16), Cu–O(1) 2.122(4), Cu–
O(2) 2.106(4), P(1)–C(41) 1.821(6), P(1)–C(51) 1.822(6), P(1)–
C(61) 1.823(5), P(2)–C(71) 1.820(6), P(2)–C(81) 1.824(6), P(2)–
C(91) 1.827(5), O(1)–C(1) 1.241(9), O(2)–C(21) 1.185(7), C(1)–
C(2) 1.618(12), C(1)–C(10) 1.296(11), C(2)–C(3) 1.333(12), C(3)–
C(12) 1.580(13), C(4)–C(5) 1.479(19), C(4)–C(12) 1.207(13), C(5)–
C(6) 1.323(16), C(6)–C(13) 1.507(13), C(7)–C(8) 1.482(13), C(7)–
C(13) 1.287(13), C(8)–C(9) 1.356(12), C(9)–C(10) 1.509(13),
C(10)–C(11) 1.390(10), C(11)–C(12) 1.385(10), C(11)–C(13)
1.421(11), C(21)–C(22) 1.554(11), C(21)–C(30) 1.400(10), C(22)–
C(23) 1.300(13), C(23)–C(32) 1.512(12), C(24)–C(25) 1.537(14),
C(24)–C(32) 1.274(11), C(25)–C(26) 1.329(14), C(26)–C(33)
1.502(11), C(27)–C(28) 1.505(14), C(27)–C(33) 1.242(12), C(28)–
C(29) 1.385(13), C(29)–C(30) 1.392(10), C(30)–C(31) 1.438(9),
C(31)–C(32) 1.360(10), C(31)–C(33) 1.409(10). Selected bond angles
(8): P(1)–Cu–P(2) 127.59(6), P(1)–Cu–O(1) 114.08(13), P(1)–Cu–
O(2) 102.84(14), P(2)–Cu–O(1) 107.14(13), P(2)–Cu–O(2)
101.03(14), O(1)–Cu–O(2) 99.10(20), Cu–P(1)–C(41) 113.37(18),
Cu–P(1)–C(51)113.84(19),Cu–P(1)–C(61)116.07(19),C(41)–P(1)–
C(51) 105.0(3), C(41)–P(1)–C(61) 102.8(3), C(51)–P(1)–C(61)
104.45(25), Cu–P(2)–C(71) 115.54(17), Cu–P(2)–C(81) 110.66(18),
Cu–P(2)–C(91) 115.81(18), C(71)–P(2)–C(81) 104.90(25), C(71)–
P(2)–C(91) 103.49(25), C(81)–P(2)–C(91) 105.34(25), Cu–O(1)–
C(1) 137.2(5), Cu–O(2)–C(21) 156.1(5), O(1)–C(1)–C(2) 117.5(6),
O(1)–C(1)–C(10) 134.1(9), O(2)–C(21)–C(22) 115.8(6), O(2)–
C(21)–C(30) 131.7(7).
˚
The two coordinated phenalenones, each within 0.08 A
deviations in a plane calculation, make an interplanar angle
of 16.1(1)8. The phenalenone solvate is planar to less than
˚
0.10 A and virtually parallel to the O2–phenalenone (with
an interplanar angle of 1.8(2)8). It is sandwiched by two O2–
phenalenone moieties that are inversion-related, the distance
from C108 to the plane of O2–phenalenone being 3.525(4)
˚
A. These results strongly suggest that there is a p–p inter-
action between the O2–phenalenone and the phenalenone
solvate in the crystalline state (cf. the interlayer distance in
˚
graphite is 3.34 A [21]). The Cu–P1 distance of 2.237(2)
˚
˚
A and the Cu–P2 distance of 2.243(2) A are very close to
the corresponding Cu–P distances in the bromobis-
(triphenylphosphine)copper(I) hemibenzenate of 2.282(3)
˚
˚
and 2.263(3) A [22]. The Cu–O1 distance is 2.122(4) A
and the Cu–O2 distance is 2.106(4) A. They are believed to
˚
be the first tetracoordinate, terminal Cu(I)–O bond lengths
with neutral ketonic O atoms instead of being derived from
the more common anionic alkoxides. For comparison, the
Cu(I)–O distances in [Cu(OPh)dppe]2(m-dppe) have been
structure of complex 9 consists of discrete (Ph3P)2-
˚
reported to be 2.023(5) A where Cu(I) is also tetrahedron
q
y
Cu(phenalenone)24 cations, BF anions and 0.5 equiv.
phenalenone solvate molecules arranged in the space group
of P-1. The phenalenone solvate occupies a crystallographic
inversion center (the atomic fractional coordinates of the
center carbon C108 are 0, 0.5, 0.5) and is hence disordered.
The structural parameters among atoms of the phenalenone
solvate are not reliable enough and are not used in compari-
sons accordingly. The BF4y anions are tetrahedral with nor-
in coordination and the phenoxo group also employs the
terminal bonding mode [23].
4. Supplementary material
Tables of crystal data and refinement details, atomic coor-
dinates, anisotropic thermal parameters, bond distances and
bond angles, torsion angles, and plane calculations for com-
plex 9 (10 pages) are available from S.L. or L.-K.L.
˚
mal B–F distances ranging from 1.240(11) to 1.293(10) A.
The (Ph3P)2Cu(phenalenone)2q cations exhibit in the solid
state a distorted tetrahedron for the central Cu coordination.
The six angles around the Cu(I) center range from /O1–
Cu–O2 of 99.1(2)8 to /P1–Cu–P2 of 127.6(1)8. The three
atom plane made of Cu, P1 and P2 is perpendicular to the
three atom plane made of Cu, O1 and O2. O1 is displaced at
Acknowledgements
We thank the National Science Council of the Republic of
China (Taiwan) for the kind financial support of this work.

40
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