620 Inorganic Chemistry, Vol. 16, No. 3, 1977
Ibers et al.
Contribution from the Department of Chemistry, Northwestern University, Evanston, Illinois 60201, and the Department of Synthetic Chemistry, Faculty of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Japan
Structure of Bis( triphenylphosphine)(N-ethoxycarbonyldithiocarbimato)palladium(II), Formed by the Reaction of Excess Ethoxycarbonyl Isothiocyanate with Palladium( 0) in the Presence of Triphenylphosphine J. AHMED,la KENJI ITOH,lb ISAMU MATSUDA,lb F U J I 0 UEDA,lb YOSHIO ISHII,lb and JAMES A. IBERS*la Received September 1, 1976
AIC60656A
When a large excess of EtOCONCS is added to Pd(0) complexes in the presence of PPh3 (Et = C2HS,Ph = C6H,), a compound of composition Pd(S2CNCOOEt)(PPh3), is isolated. On the basis of an x-ray diffraction study the compound The compound crystallizes in is shown to be bis(triphenylphosphine)(N-ethoxycarbonyldithiocarbimato)palladium(II). space group C,'-P1 of the triclinic system with two molecules in a unit cell of dimensions a = 13.371 (2) A, b = 13.741 (3) A, c = 10.995 (2) A, a = 93.85 (I)", = 113.74 (l)', y = 95.30 (l)", and V = 1829 A3. The structure has been solved by the heavy-atom method and refined by full-matrix least-squares techniques to a final value of the conventional R index on Fo of 0.042 based on 5794 unique reflections having F: 1 3u(FO2)collected by counter methods. The Pd atom is coordinated to two P atoms from the PPh3 groups and to two S atoms of the S,C=NCOOEt dithiocarbimato ligand in approximately a square-planar fashion. The Pd-P distances are 2.306 (1) and 2.333 (1) A, and the Pd-S distances are 2.316 (1) and 2.343 (1) A. The S-Pd-S angle is 75.03 (4)', while the P-Pd-P angle is 98.89 (4)". All five atoms in the inner coordination sphere are within 0.1 8, of the best least-squares plane defined by these atoms. The S-C bond lengths are 1.742 (4) and 1.754 (4) A and the C-N bond length is 1.282 (5) A. The comparable parameters within the inner coordination sphere agree very well with those found in the bis(N-cyanodithiocarbimato)nickelate(II) anion. In addition, these parameters differ but little from those of typical dithiocarbamate complexes.
Introduction Our recent studies of the reactions of isocyanates2 and isothiocyanate~~,~ with Rh(1) and Pd(0) complexes have revealed a varied and rich chemistry. That this chemistry can also be surprisingly complex is illustrated by the reactions of EtOCONCS5 with Pd(0) in the presence of phosphines. When EtOCONCS is added in small excess to Pd2(dba)3CHC135s6 and PPh3 in benzene, a complex of composition Pd(SCNCOOEt)(PPh,), (I) is obtained in 80% yield. The complex is somewhat unstable in solution because of its tendency to lose the isothiocyanate ligand, but it is stable in the solid state; mp 108-112 "C dec; IR (KBr) v(C=O) 1700 and v(C=N) 1625 cm-'. The structure of the complex is probably Ph,P Ph,P
\
C=N / I
/ Pd \
/
COOEt
I
S I
However, when the reaction is carried out with a (5-6)-fold excess of EtOCONCS, a complex of composition Pd(S2CNCOOEt)(PPh,), (11) is obtained in 78% yield. This complex is very stable both in solution and in the solid state; mp 200-202 OC dec; IR (KBr) v(C=O) 1706 and u(C=N) 1537 cm-'. The NMR spectra of these two complexes show only minor differences. On the basis of these spectroscopic results reasonable formulations for I1 are COOEt
1
N Ph,P Ph,P
II
\
I
Pd
C I \
\I
S IIa
Ph,P S
Ph,P
\
I
S
Pd
I \ \ I
C=N
I
COOEt
S
IIb
The results of an x-ray diffraction study of compound I1 are presented here which indicate that it is correctly formulated as shown in IIb, a dithiocarbimato complex of Pd(I1). Experimental Section Preparation of Pd(S2CNCOOEt)(PPh3)2.PPh, (400 mg, 1.53 mmol), Pd2(dba)j.CHC13 (200 mg, 0.193 mmol), and benzene (20 ml) were stirred under Ar at rmm temperature for 1.5 h. EtOCONCS (353 mg, 2.69 mmol) was slowly added to the resultant orange
homogeneous solution. The color of the solution turned yellow. The solution was stirred for 2 h at room temperature. Solvent was removed under reduced pressure to give a reddish brown oil, to which ether (20 ml) was added. Pale yellow, crude product was isolated in 78% yield (283 mg) and was recrystallized from a mixed solvent of dichloromethane and ether to obtain yellow prisms: mp 200-202 OC dec; IR (KBr) 1706 (u(C=O)) and 1537 (u(C=N)) cm-I; NMR (CDCI3) 6 1.18 (t, 3 H, CHJ, 4.08 (q, 2 H , CH,) with J = 7.0 Hz, and 7.24 (m, 30 H, aromatic). Anal. Calcd for C40H35N02P2PdS2: C, 60.49; H, 4.44; N,1.76; P, 8.07. Found: C, 60.41; H, 4.42; N, 1.98; P, 8.01. This complex was also prepared from the reaction of Pd(SCNCOOEt)(PPh,), (50.6 mg,0.066 mmol) with EtOCONCS (83.6 mg, 0.638 mmol) by stirring the mixture 3 h at room temperature. The resultant yellow powder (3 1.2 mg) yielded the same IR and NMR data as above. Preparation of P ~ ( S C N C O O E ~ ) ( P P ~PPh3 I ~ ) ~ .(800 mg, 3.05 mmol) and Pdz(dba),-CHCI3(400 mg, 0.386 mmol) were stirred in benzene (20 ml) under Ar at room temperature. EtOCONCS (163 mg, 1.24 mmol) was added to the orange homogeneous solution. The reaction mixture immediately turned yellow. It was stirred for 2 h at room temperature. Evaporation of the benzene followed by the addition of ether (20 ml) caused the precipitation of pale yellow crystals in 80% yield. The complex is not stable in solution. Therefore, recrystallizationwas achieved from methylene chloride which contained a few drops of EtOCONCS and ether mixed solvent; mp 108-1 1 2 "C dec: IR (KBr) v(C=O) 1700 and u(C=;U) 1625 cm-'; N M R (CDC13) T 2.8 (30 H, aromatic), 6.07 (q, 2 H, C H 2 0 ) , and 8.87 (t, 3 H , CH,). Anal. Calcd for C40Hj5N02SP2Pd:C, 63.04; H, 4.63; N, 1.84. Found: C, 62.98; H , 4.67; N, 1.83. Collection of X-Ray Intensity Data. Preliminary Weissenberg and precession photographs failed to reveal any symmetry other than the expected center of inversion and the crystal was assigned to the triclinic system. General procedures for the determination of unit cell parameters and for the collection of intensity data have been given p r e v i o u ~ l y . ~The ~ ~ compound Pd(SZCNCOOC2H5)(PPh3)2,C40H35NOZP2PdS2, has mol wt 794.21 and crystallizes in a Delaunay reduced cell of dimensions a = 13.371 (2) A, b = 13.741 (3) A, c = 10.995 (2) A, a = 93.85 (I)', fl = 113.74 (l)", y = 95.30 (l)', and V = 1829 A); pc = 1.442 g/cm3 and po (by flotation in ZnC1, solution) = 1.45 (2) g/cm3. The crystal selected for data collection had approximate dimensions 0.28 X 0.48 X 0.51 mm, calculated volume 0.0237 mm3. Trial transmission factors ranged from 0.841 to 0.867, based on a linear absorption coefficient for Mo K a radiation of 7.30 cm-'; accordingly no absorption correction was deemed necessary. Data were collected on a Picker FACS-I diffractometer using Mo K a radiation monochromatized from a mosaic graphite crystal. Details of data collection include the following: aperture 2.3 mm wide X 5.0 mm high, 34 cm from crystal; takeoff angle 2.5";
Structure of Pd(S2CNCOOEt)(PPhJ2
Inorganic Chemistry, Vol. 16, No. 3, 1977 621
Table I. Positional and Thermal Parameters for Nongroup Atoms of Pd(S,CNCOOEt)(PPh,), A
....... .........*..*!....*....*.~*~~~.....**.......* .... ..... B
~!?I.........~.:*...... PO
-0~05269912ll
Sfll
0.12728ZI82l
SI21
0.038961194l
PI11
-0.114196179l -o.~i5957(801 0.40607137l 0.373341431 0.256611331 0.1607bI341 0.34883lSll 0.4754(121
PI21 0111 0121 N
Clll
C I O c131 CI4l ...a.
0.4146f141
0.2273011201 0.208439f841 0.2256571911 0.214225170l 0.257i50~721 0.186931541 0.336571391 0.24076f301
BL2
-0~22202212bl - 0 . 0 8 5 9 3 1 111
0.226721231
-0~364161111 -0~054916195l -0.3935401951 -0.~6257150l -0.04594101l -0~~Z2871461 -0.22217f451
0 . 2 6 6 1 9 1391
-0~104291691
0.36921151 0.3539 1 191
o.neio(zJi 0.1856 I231
3.95121 4.45171 6.65191 4.5317) 4.51171 12.961421
11.921501
5.911511 6.15130) 5.961311 16.11141 21.5 I221
..........*.........*.********~~~.*.......*.**,*.**...~...*..~*~.*.*,.~~.~~.~~***....*~
3.71121 6.0817l 6.96 1 01 3.53151
3.76161 8.701331 8.481371 6.081251 3.771231 5,791321 16.6f161 35.3 I25 I
*...!E.**+
,ItS.......,..I!!
...L
.*
....Pt?.,..
5.07141 8.49f i l l
0.51111
Z.18IZl
1,19161
2.161 71
1.06171
8,921121
1.58161 0.56151 0.46 1 5 I
4.nz191
1.40181
6.541101 6.271101 21.161131 57.21101 16.601611 11.481521 23.4flOI 84.91621
78.6 (561
4.381341
2 . t 0 f 71 1.931 71 5.83(451 -13.181781
1.061EZI
6.31138l
i.oi1zii
4.171331
0.541311 o.iarz71
6.611521
0.851451
5.371 311
1,381281
2.7f12l -io.afzii
-14.7 1 2 1 1 -34.1 1 2 8 1
.
0.56121
0.59 (61 0.65161
2.761 391 -8.911651
7.0 1251 in.4r331
I.....*........,*...**,..........L.
STANDARD O E V I A T I O N S I N T H E L E A S T S I G N I F I C A N T F I G U R E f S I ARE G I V E N I N P A R E N T H E S E S I'J T H I S AND A L L SUBSEQUENT T A B L E S . 'THE 2 2 2 FORM OF THE A N I S O T R O P I C T H E l N b L € \ L I P S 0 1 0 1 s t E X P I - 1 B l l H +822K *E33L * 2 B 1 2 H K r 2 B 1 3 H L 1 2 B 2 3 K L l 1. THE O U A N T I T I E S G I V E N I N THE T b B L E
'ESTIMATED
ARE T H E THERMAL C O E F F I C I E N T S X
2
IOu. RI
Figure 1. Perspective view of the Pd(S2CNCOOEt)(PPh3), molecule showing the numbering scheme. The vibrational ellipsoids are drawn at the 50% probability level exce t for atoms 0(2), C(3), and C(4), which are drawn with B = 3.0 and for the H atoms.
i2,
scan speed 2.0°/min; scan range from 0.7" below the Kcv, peak to 0.8" above the Ka2 peak; background counts for 10 s at each end of the scan range; 6471 unique data collected out to 50' in 20, past which point few intensities were above background; six standard reflections collected every 100 reflections showing variations within counting statistics. Solution and Refinement of the Structure. By using a value for p of 0.04' the data were processed to yield 5794 unique reflections having F: > 3u(F>). Only these reflections were used in subsequent calculations. Computer programs, sources of scattering factors and anomalous terms, and calculational procedures have been noted previo~sly.~ The positions of the Pd and the four atoms immediately surrounding it were determined from a sharpened, origin-removed Patterson function. The usual procedure of full-matrix least-squares refinements interspersed with difference Fourier syntheses revealed the positions of all of the remaining nonhydrogen atoms. Space group C,'-Pf was assumed. After initial anisotropic refinement of all nonhydrogen nongroup atoms a difference Fourier synthesis revealed the positions of all of the hydrogen atoms of the phenyl groups and the hydrogen
atoms of the methine carbon atom, as well as the positions of a set of six half hydrogen atoms on the methyl group. The location of these hydrogen atoms justifies the assumption of the centrosymmetric space group. The final refinement model of 181 variables included fixed contributions for the H atoms (C-H = 0.95 A, B ( H ) = B,,,(C) + 1 A*) and anisotropic parameters for all nonhydrogen atoms except for the carbon atoms of the six phenyl rings which were refined isotropically, each phenyl ring being refined as a rigid group. This refinement converged to values of R and R, of 0.042 and 0.064, respectively, and to an error in an observation of unit weight of 2.36 e. The largest peak on the final difference Fourier map is 0.9 e/A3, about 25% the height of a typical C atom. All major peaks on this map were associated with the C atoms of the phenyl groups, a normal observation after rigid-body refinement. Although the thermal parameters of portions of the ethoxy moiety are high enough to suggest some disorder, the final difference Fourier map showed no significant features in that area. Examination of xw(lFol - IF0l)', the function minimized in the refinements, as a function of IFo[,setting angles, and Miller indices revealed no unusual trends. Of the 677 reflections having F,Z < 3u(F:) and omitted from the calculations, ten have Q > 447:) and five have Q > 5u(F>), where Q = IF: - F21. The final positional and thermal parameters for the nongroup atoms are given in Table I. Table I1 contains information on the atoms of the rigid groups. Table I11 presents data on the idealized hydrogen atoms. Root-mean-square amplitudes of vibration are presented in Table 1V.I' The values of 10IFoland 10IFcl(in electrons) are given in Table V."
Discussion The structure determined in this study is shown in perspective view in Figure 1 together with the labeling scheme. The molecular structure corresponds to IIb; the compound is bis( triphenylphosphine)(N-ethoxycarbonyldithiocarbimato)palladium(I1). Figure 2 shows a stereoview of the two well-separated molecules in the unit cell. Figure 3 presents a projection of the molecule, together with some important bond distances and angles. A more complete listing of distances and angles may be found in Table VI. As judged by the agreement among the six P-ring C distances, the standard deviations, as estimated from the inverse matrix, are reasonable. However, owing to high thermal motion of the atoms of the ethoxy group, bond distances and angles in this portion
Figure 2. Stereoview of a unit cell of Pd(S2CNCOOEt)(PPh3)2. The x axis goes from left to right, the y axis goes into the paper, and the axis goes from bottom to top. The vibrational ellipsoids are drawn at the 20% probability level except for 0 ( 2 ) , C(3), and C(4) (3.0 A2) and the H atoms (1.0 A2).
z
622 Inorganic Chemistry, Vol. 16, No. 3, 1977
Ibers et al.
Table 11. Derived Parameters for the Rigid-Group Atoms and RigidGroup Parameters of Pd(S ,CNCOOEt)(PPh,),
..........
t!~.l..~....*~**.*,**.~** RlCl
........
~L!9 ..*....~Iq?..11...~~.***.*
-0.01865120)
0 , 1 7 7 8 1 (191
0.103331211
2.96171
2
!.l.........*.Cf.......*.,*.?:~
R4Cl
-0.35080
1181
..I.
0.24187l201
-0.38400
1281
2.9817)
RlCZ
0.078041221
0.24133117l
0.17571127l
3.80181
R4C2
-0.376211211
0.31481 I 1 7 1
-0.31116 I 2 8 1
3.84181
RlC3
0.14871lZO~
0.22297121)
0.302821271
4.50 19)
R4C3
-C.478491241
0.305431211
-0.30465 132)
4.84110)
RlC4
0.122681231
O.lLlOl1231
0.35753122l
4.84110 I
Q4C4
- 0 . 5 5 5 2 6 1191
0.22312l241
-3.37c971351
F.67111)
R1C5
0.025981251
0.077561191
0.28515128l
4.94 I1 0 )
R4C5
-0.52979121)
0,15019119)
-0,44380(31)
4.8711CI
RlC6
-0.04468120)
0.0 9593 1 1 8 )
0.158041271
3.74 I 8 1
Q4C6
-0.42756 ( 2 3 )
0.15956 I 1 8 1
-0.455 31 1 2 3 1
3.9318)
R2Cl
-0.14668123)
0.32730116)
0.00885126l
2.92171
R5Cl
-0.207591221
0.583571161
-3.437221291
3.1617)
RZCZ
-0.133831251
0.4150212OI
-0.042731251
3.79181
45C2
-0.302531181
0.421321211
- 0 . 5 1 7 0 2 131)
4.25 19)
R2C3
-0.153041281
0.50215116)
0.011391311
4.901101
95C3
-0.294761211
0.51427122)
-2.55816
5.141101
R2C4
-0.185091291
0.50156l171
0.11710
5.01110)
R5C4
-0.19225
0.569471181
-3.51949134)
5.041111
R2C5
-0.197941271
01413831211
0.16868l26l
4.631101
R5C5
-0.0971OlZt)
0.531731211
- G . 4 3 9 6 9 1341
5.c41101
R2C6
-0.178731251
0.326701171
0.11456127)
3.6318I
R5C6
-O.10487118~
l.4387SIZll
-6.39855t291
4.0318)
RSCI
-0.23279117)
O.12OElIl61
-0
2.80 171
R6Cl
-0.245361231
0.17622(18 I
-6.54569121)
2.951 71
R3CZ
-0.3321112OI
0.13S66IlSl
-0.10328127)
2.94171
R6C2
-0.30473124)
0.202571161
-9.67192 126)
3.69181
R3C3
-0.417261171
0.05732 119)
-0.14311130)
3.75181
Q6C3
-0.33024124)
0.11673121)
-0.7853012Ol
4.3019)
R3C4
-0.4~3091201
-0.0 355 8 1 1 6 )
-0.189831311
4 . 4 3 I91
R6C4
-0.294371261
0.044551191
-3.772431231
4.3419)
R3C5
-0.30377124l
-0.04953 1 1 5 )
-0.196711311
4.70 1 1 0 1
R6C5
-0.23299126)
3.018191161
-3.64619129)
4.30 1 1 0 )
R3C6
-0.21862118l
0 . 0 2 8 1 2 1191
-0.15688130)
3.81111)
*.*.......**.*..***.*...*.*.*.**~...*...**.**
a
1321
1101 7 1 2 7 )
1271
(31)
'..*.****..*.....*.*~*.*.......*..~....~..*.*...........*.*....*.... R6C6
-0.297491241
0.3R403120)
-3.53282122l
4.17191
RIG10 GROUP PURAMETESS GROUP
X
*.*.*.*..*
e..
A
E
.....*
RING 1
0.052011161
.....
................*.*.. .........**......*
L
V
....I
OELTU
. E * * . * . l . * . * . l . . . ~ * . * . * *
0,15945114)
R
EPSILON
ETU
a.....=
1
0.23043 119)
-0.6822118) -:.4c4c1321
...I
2.94171171
e.......
D.3305119)
RING 2
-0.165851161
0.41443 I141
0.06297 I 1 9 1
RING 3
-0.31794 1151
0.04257 1 1 3 )
-0~150001171
0.23250115)
-0.37748
-2.5985110)
2.58301221
0.47652 1 1 5 1
-0.47836120)
1 , 5 3 2 6 1 161
3.0516120)
-C1364212C)
0.11038114l
-0.65906 1191
6.5673126)
2.7168116)
855 1 2 0 )
RING 4
-0.45303116)
RING 5
-0.1993
RING 6
-0.868861151
2 1 171
..*.*..*...*....*.**.......*.~.*.~*..*~.**~~~*.~..*~~~.~~.... 'X
+ V*,
SIfOH,'AN"
An0 2
-2.61571 1 3 1
-0.3C6F1191
1191
2 . 0 8 0 0 1 32)
2.18351161
0.72171161
-3.16621191
- 2.0
"..*~*~.**.*.**.~~**~*...*~*~....*..**.**.~..~....*.*~+~.*...*..~~*~*
ARE THE FR4CTIONAL COOROIUPTES OF THE O R I G I N O F THE R I G I O GROUP.
ETPF9AOIUNS) H A V E SEEN OEFIHED PREWIOUSLVI S . J .
LA PLICA U N O J.A.
8
THE R I G I O :ROUP
ORIENTATION ANGLES DELTU,
IEEQSr U C T b CSVSTbLLOGQ..
EP-
13, 5 1 1 1 1 9 6 5 1 .
Table 111. Idealized Positional Coordinates for Hydrogen Atoms ~
Atom
H,C(3) H,C(4) HzC(4) H 3C(4)
X
Y
0.096 0.215 0.171 0.009 -0.110 -0.113 -0.146 -0.199 -0.220 -0.187 -0.342 -0.485 -0.461 -0.294 -0.151
0.297 0.266 0.129 0.022 0.05 3 0.415 0.562 0.561 0.414 0.267 0.198 0.067 -0.088 -0.112 0.018
0.510 0.466 0.350 0.405
0.428 0.395 0.384 0.291
~
~
~~~
X
Y
Z
Phenyl Groups 0.139 HR4CZ 0.353 HR4C3 0.445 HR,C4 0.323 HR4C5 0.109 HR4Cti -0.116 HR,CZ -0.025 HRSC, 0.154 HR,C4 0.241 HRSC, 0.150 HR,Cti -0.071 WCZ -0.1 38 HR6C3 -0.216 HR6C4 -0.228 HRtiC, -0.162 HR6C6
-0.324 -0.496 -0.625 -0.582 -0.410 -0.373 -0.360 -0.187 -0.027 -0.040 -0.330 -0.372 -0.312 -0.208 -0.165
0.371 0.356 0.217 0.094 0.109 0.384 0.540 0.634 0.570 0.414 0.265 0.155 -0.000 -0.045 0.066
-0.266 -0.255 -0.366 -0.488 -0.499 -0.544 -0.613 -0.548 -0.413 -0.344 -0.681 -0.872 -0.850 -0.638 -0.447
Ethyl Group 0.077 H,13(3) 0.265 H , C(4) 0.147 H;:C(4) 0.196 H; C(4)
0.527 0.469 0.354 0.398
0.317 0.339 0.31 1 0.421
Z
of the molecule are not representative. The Pd atom is four-coordinate, being bound in roughly a square-planar fashion to the P atoms of the PPh3 groups and to the two S atoms of the dithiocarbimate ligand. Table VI1 lists some important least-squares planes and interplanar angles. Note that the PdS2P2portion of the molecule is essentially planar (plane no. 3), exhibiting only a very small tetrahedral distortion. Distortion from square-planar coordination about Pd(I1) occurs mainly as a result of the small, S(1)-Pd-S(2) bite angle of 75.03 (4)", with a corresponding P(l)-Pd-P(2) angle of 98.89 (4)'. The Pd-P distances of 2.306 (1) and 2.333 (1) A appear to differ significantly from one another, as do the Pd-S distances of 2.316 (1) and 2.343 (1) A. This may result from packing effects: the phenyl groups on atom P(2) are tilted more toward the P(2) and S(2) atoms than are those attached to atom P( 1) toward the P ( 1)
Atom
0.086 0.264 0.146 0.198
and S( 1) atoms. In any event, the Pd-P distances are typical of those found in a variety of Pd complexes."-19 Moreover, the Pd-S distances are close to those found in Pd(CS2)(PPh3)?0 (2.305 (1 1) A), in Pd2(S2CSCMeJ2(SCMe3)*(2.313 (3) and 2.330 (3) A), a dimer,*' and in the trimers2'xz2Pd(S2CPh)2(2.320 (3)-2.343 (3) A) and Pd,(S,CSEt),(SEt), (2.331 (4)-2.349 (5) A). As predicted from an infrared spectral study of N cyanodithiocarbimate~'~and as found in the Ni(S2CNCN)22anion24the metal-S2C ring system in the present complex is essentially planar (plane no. 2 , Table VII). A comparison of the inner portion of the metal-dithiocarbimate system here with that found in the Ni(S2CNCN)22-anionz4 shows reasonable agreement (S-C = 1.754 (4) and 1.742 (4) vs. 1.69 (2) and 1.75 (3) A; C=N = 1.282 (5) vs. 1.29 (3) A; S-C-N = 128.2 (4) and 123.3 (4) vs. 132 (2) and 120 (2)'). As noted
Structure of Pd(S2CNCOOEt)(PPh3),
Inorganic Chemistry, Vol. 16, No. 3, I977 623
Table VI. Selected Bond Distances (A) and Angles (deg) in Pd(S ,CNCOOEt)(PPh,), Distances 2.316 (1) Pd-S(2) 2.306 (1) Pd-P(2) 1.754 (4) S(2)4(1) 1.832 (2) P(2)-R4C, 1.822 (3) P(2)-RsC, 1.815 (2) P(2)-R,Cl 1.180 (6) C(3)€(4) 1.283 (7) 0(2)€(3) 1.282 (5) NC(2) 2.837 (2)
2.343 (1) 2.333 (1) 1.742 (4) 1.842 (3) 1.839 (3) 1.831 (3) 1.668 (31) 1.510 (18) 1.377 (7)
Angles 75.03 (4) P(l)-Pd-P(2) 94.27 (4) S(2)-Pd-P(2) 168.66 (4) S(l)-Pd-P(Z) 87.96 (14) P d S ( 2 ) C ( 1 ) 117.2 (1) Pd-P(2)-R4C, 116.1 (1) Pd-P(2)-RsC, 109.8 (1) Pd-P(2)-R6C, 99.1 (1) R4C,-P(2)-RsC, 104.0 (1) R4Cl-P(2)-R6C1 109.5 (1) R,C,-P(2)-R,C1 108.5 (2) C(2)-0(2)C(3) 119.6 (5) NC(2)-0(1) 128.2 (4) NC(l)-S(Z) 96.2 (1.2) 0(1)€(2)-0(2) 110.6 (5)
S(l)-Pd-S(Z) S( l)-Pd-P( 1) P( l)-Pd-S(2) Pd-S(l)C(l) Pd-P(1)-R ,C , Pd-P(1)-R,C , Pd-P(l)-R,C R,C,-P(l)-R,C, R ,C I -P( 1)-R,C R,C ,-P( l)-R,C S(1)4(1)4(2) C(l)-NC(2) NC(l)-W) C(4)C(3)-0(2) 0(2)C(2)-N
C(l)-S(l)-Pd-S(2) PdS(2)€(1)-S(l)
Torsion Angles 6.8 (1) S(l)-PdS(2)€(1) 9.3 (2) S(Z)C(l)-S(l)-Pd
98.89 (4) 92.00 (4) 166.56 (5) 87.41 (14) 123.5 (1) 112.13 (8) 109.77 (10) 101.9 (1) 101.8 (1) 106.1 (1) 122.8 (9) 127.4 (6) 123.3 (4) 121.8 (6)
Figure 3. A molecule of Pd(SzCNCOOEt)(PPh3)2 with selected bond distances and angles. H atoms are omitted for clarity.
the actual distances and angles involved, suggested to them that the best hybrid descriptions of the dithiocarbimate (111) and dithiocarbamate (IV) ligands in that instance were
-6.9 (1) -9.4 (2)
-S
-S \
by Cotton and Harris24there are no significant differences between any of the corresponding distances or angles in the central Ni(S2CN)* portions of their Ni(S2CNCN)2- dithiocarbimate anion and an N,N-diethyldithiocarbamate complex of Ni, Ni(S2CNEt2)2.25These results, together with
/
C”
-S
I
-S
\
I
/C=N;
111
IV
There appear to be no palladium-dithiocarbamate structures with which to compare the present structure. But our results
Table VU. Weighted Least-Squares Planes Deviations from Planes,” A Plane Atom
1
Pd S(1) S(2) P(1) P(2) O(1) N C(1)
0.392 0.000 (1) 0.000 (1) 0.57 0.85 -0.77 0.004 (4) -0.008 (4)
2 0.0006 (3) -0.011 (1) -0.013 (1) -0.14 0.15 -0.03 0.47 0.190 (4)
3 0.0004 (3) 0.076 (1) -0.094 (1) -0.042 (1) 0.045 (1) 0.08 0.47 0.19
4 0.0023 (3) -0.042 (1) -0.053 (1) -0.10 0.18 -0.13 0.384 (4) 0.1 34 (4)
5
6
0 (0)
0 (0) 0 (0) 0 (0)
-0.110 0.129 0 (0)
-0.15 0.15 0.01 0.49 0.21
0 (0)
-0.13 -0.47 -0.19
Equations of Planesb Plane
A
B
C
D
1 2 3 4 5 6
-1.838 0.925 0.947 0.655 -0.945 1.014
13.468 13.293 13.105 13.327 -13.016 13.280
1.417 0.537 1.123 0.655 -1.366 0.500
2.451 2.853 2.679 2.847 -2.606 2.854
’
Dihedral Angles, Deg
a
Ax
Planes
Angle
Planes
Angle
1-2 1-3 14 1-5 1-6 2-3 2-4 2-5
11.9 12.5 10.7 167.1 12.3 3.4 1.2 175.2
2-6 3-4 3-5 3-6 4-5 4 6 5-6
0.4 3.5 178.6 3.5 175.2 1.6 175.2
If no standard deviation is given for the distance of an atom from the plane, the atom was not used to define the plane. + By + Cz - D = 0, where x , y , z are in triclinic coordinates.
Plane equation:
624 Inorganic Chemistry, Vol. 16, No. 3, 1977
suggest that I11 is an adequate description for the present dithiocarbimate structure as well. The mechanism of formation of the present complex, especially the abstraction of the “extra S atom” from the medium, remains unaccounted for. The compound can be formed by reaction of excess EtOCONCS with the initially formed Pd(SCNCOOEt)(PPh3)2. Whether the organic fragment, EtOOCNC, is trapped by PPh3 is a possibility that is now under study. Acknowledgment. This research was supported by UNESCO and by the Ministry of Education of Japin. J.A. acknowledges with thanks receipt of a UNESCO fellowship, while on leave from the University of Islamabad, Pakistan. Registry No. Pd(S2CNCOOEt)(PPh3)2, 61202-76-4; Pd(SCNCOOEt)(PPh3)2, 61202-77-5; Pd2(dba)3,52409-22-0. Supplementary-Material Available: Table IV, the root-mean-square amplitudes of vibration, and Table V, the structure amplitudes (41 pages). Ordering information is given on any current masthead page.
References and Notes (1) (a) Northwestern University. (b) Nagoya University. (2) S. Hasegawa, K. Itoh, and Y. Ishii, Znorg. Chem., 13, 2675 (1974). (3) M. Cowie, J. A. Ibers, Y . Ishii, K. Itoh, I. Matsuda, and F. Ueda, J . Am. Chem.Soc.,97,4748 (1975); M. Cowieand J. A. Ibers, Znorg. Chem., 15, 552 (1976). (4) Y. Ishii, K. Itoh, I. Matsuda, F. Ueda, and J. A. Ibers, J . Am. Chem. Soc., 98, 2014 (1976).
Yasufuku, Aoki, and Yamazaki Abbreviations: Ph, phenyl; dba, dibenzylideneacetone; Et, ethyl: Me, methyl T. Ukai, H. Kawazura, Y . Ishii, J. J. Bonnet, and J. A. Ibers, J . Organomet Chem., 65, 253 (1974). P. W. R. Corfield, R. J. Doedens, and J. A. Ibers, Znorg. Chem.. 6 , 197 (1967) R. J. Doedens and J. A. Ibers, Znorg. Chem., 6, 204 (1967). A P. Gaughan, Jr., and J. A. Ibers, Inorg. Chem., 14, 3073 (1975). Supplementary material. J. Fayos, E. Dobrzynski, R. J. Angelici, and J. Clardy, J . Organomet. Chem, 59, C33 11973). R. Mason and P.’O. Whimp, J . Chem. SOC.A , 2709 (1969). T. Debaerdemaeker, A. Kutoglu, G. Schmid, and L. Weber, Acta Crystaliogr., Secr. E , 29, 1283 (1973). N . A. Bailey and R. Mason, J . Chem. Sot. A , 2594 (1968). G. Beran, A. J. Carty, P. C. Chieh, and H. A. Patel, J . Chem. Sot., Dalton Trans.. 488 11973). A. J . Carty, Pl C.~Chieh,N. J. Taylor, and Y. S. Wong, J . Chem. Soc., Dalfon Trans., 572 (1976). J . A. McGinnety, J . Chem. Soc., Dalton Trans., 1038 (1974). J. J. Daly, J . Chem. Soc., 3799 (1964). P. M. Maitlis “The Organic Chemistry of Palladium”, Val. I. Academic Press, New York, N.Y., 1971, p 38. T.Kashiwagi, K.Yasuoka. T. Ueki, N. Kasai, M. Kakudo, S.Takahashi. and N. Hagihara, Bull. Chem. Soc. Jpn., 41, 296 (1968). J. P. Fackler, Jr., and W. J. Zegarski. J. Am. Chem. Soc., 95,8566 (1973). M. Bonamico and G. Dessy. Chem. Commun., 483 (1968); M. Bonamico, G . Dessy, V. Fares. and L. Scaramuzza, J . Chem. Soc., Dalfon Trans., 2250 (1975). J . P. Fackler, Jr., and D. Coucouvanis, J . Am. Chem. Soc., 88, 3913 (1966). F. A. Cotton and C . B. Harris, Inorg. Chem., 7, 2140 (1968). M. Bonamico, G . Dessy, C. Mariani, A. Vaciago, and L. Zambanelli, Acta Crystallogr., 19. 619 (1965).
Contribution from The Institute of Physical and Chemical Research, Wako-shi, Saitama 351, Japan
Crystal and Molecular Structure of 1,l’-(Tetraphenyl- epheny1ene)ferrocene KATSUTOSHI YASUFUKU,* KATSUYUKI AOKI, and HIROSHI YAMAZAKI
Receiced September 1, 1976
AIC606472
1,l’-(Tetraphenyl-o-phenylene)ferrocene,C40H28Fe,crystallizes in the monoclinic of space group P21/,, and four molecules in the unit cell with a = 24.342 (7), b = 10.959 (9,c = 11.397 ( 5 ) A,and p = 112.69 (3)’. A single-crystal x-ray structural analysis has been completed. The structure was solved by conventional Patterson, Fourier, and least-squares refinement techniques. All atoms, including hydrogens, have been located, the final discrepancy indices being R1 = 5.40 % and R2 = 6.25 % for 2939 independent reflections. The cyclopentadienyl rings in the ferrocene moiety are eclipsed and tilted by . 23.7’.
Introduction Reaction of 1,l’-bis(phenylethyny1)ferrocene (1) with acetylene-cobalt complexes (2) yielded 1,l’-(o-phenylene)ferrocene, (0-phenylene)- [ 2]ferrocenophane, derivatives (3). @C,CPh
+
Fe
T -
C,H.jCO(PPh,)(RC32R’)
2
Q-CECPh
1
N M R spectra exhibited a set of A2B2patterns associated with the ferrocenyl rings for 3a and 3c and two broad signals attributable to the overlap of two sets of A2B2patterns for 3b. It has been known that the splitting of the A2B2signals of the ferrocenyl protons2 and the electronic spectra, especially the band corresponding to A, 440 nm of (C5H&Fe, correlate to ring-tilt distortion angle in [m]ferr~cenophane.~ Structural features of the ferrocene and benzene moiety of 3a, a new [2]ferrocenophane with the shortest bridging group, e.g., two sp2 carbons, are of great interest in connection with the large splitting (A6 = 0.87) of the A2B2signals and A, 466 nm (e = 470) of this compound. We now report the crystal structure of 3a. Experimental Section Recrystallization of air-stable 3a, C&12*Fe, from hexane/methylene chloride gave well-formed columnar crystals suitable for x-ray studies. Precession and Weissenberg photography indicated that the crystals were monoclinic with the systematic absence of h01, h = 2n 1, and OkO, k = 2n + 1, consistent with space group P2,,,. Cell constants of a = 24.342 ( 7 ) A,b = 10.959 (5) A, c = 11.397 (5) A, and p = 112.69 (3)’ were determined from high-order reflections on a Rigaku four-circle automated diffractometer. The unit cell volume is 2805.0 A3, yielding a calculated density of 1,337 g cm-3 for M = 564.5 and 2 = 4. [The experimental density is 1.38 (10) g cm-3 by flotation
+
3a, R, R’ = Ph b, R = Ph; R’ = CO,CH, c, R , R’ = CO,CH
The structures 3 have been presented on the basis of their microanalyses and spectral properties.’ In particular, the ‘H
