The first 6a-thiathiophthen metal complex was prepared by treating M(CO_)5[PPh_2CS_2CH_2C≡CH] with a catalytic amount of secondary amine or tertiary amine; the structure of the 6a-thiathiophthen molybdenum complex is confirmed by an X-ray diffraction analysis

Lee, Gene-Hsiang

Lin, Ying-Chih

Wang, Yu

Yih, Kuang-Hway

English

Caltech Authors - Main

J. CHEM. SOC., CHEM. COMMUN., 1995 223 
Synthesis and Crystal Structure of the First 6a-Thiathiophthen Metal Complex 
[MO(CO)~PP~~I~(FL-C~H~S~) 
Kuang-Hway Yih, Ying-Chih Lin,* Gene-Hsiang Lee and Yu Wang 
Department of Chemistry, National Taiwan University, Taiwan 106, Republic of China 
The first 6a-thiathiophthen metal complex was prepared by treating M(CO)5[PPh2CS2CH2C=CH] with a catalytic 
amount of secondary amine or tertiary amine; the structure of the 6a-thiathiophthen molybdenum complex is 
confirmed by an X-ray diffraction analysis. 
With their unusual11 long S-S distances and possible aromatic 
properties of the two fused five-membered rings, the 6a- 
thiathiophthen (3,3a,4-trithiopentalene) derivatives1 have at- 
tracted considerable attention. Methods for the synthesis of 6a- 
thiathiophthen2 and arylthio- or alkylthio-derivatives3 using 
various thionation reagents such as S, H2S and P2S5 have been 
reported. Furthermore, much work has been done on the 
bonding: structure,' reactions6 and electron density deforma- 
tion7 studies on 6a-tliiathiophthen and its derivatives. However, 
no 6a-thiathiophthen metal complex has been reported. Here we 
report the high yield synthesis and the structure determination 
of the first 6a-thiathiophthen metal complex, which was 
prepared from the metal complex containing the diphenyl(S- 
prop-2-ynyl-dithiofcmnato)phosphine ligand.8 
Treatment of M(('0)5[PPh2(CS2CH2C=CH)] (M = Mo, la; 
W, 1 b) with a catalylic amount of Et3N in CH2C12 yields the 6a- 
thiathiophthen metal complexes [M(CO)5PPh2]2(p-C5H2S3) (M 
= Mo, 2a; W, 2b) at room temperature (Scheme 1). Complex 
2a is isolated as a red microcrystalline powder by recrystalliza- 
tion from hexane-CH2CI2 in ca. 85% yield. The spectroscopic? 
and analytical data of 2a are in agreement with the formulation. 
The FAB mass spectrum of 2a shows a base peak at mlz 721, 
corresponding to [ M O P P ~ ~ I ~ ( ~ - C ~ H ~ S ~ ) + ,  formed by loss of the 
ten CO groups from 2a. The IR spectrum of 2a shows two 
terminal carbonyl stretches at 2073 and 1924 cm-1, a typical 
pattern for a LM(C0)S unit in octahedral geometry. The 1H 
NMR spectrum of 2a exhibits a doublet at 6 7.90 (3JPpH = 7.2 
Hz) attributed to the two equivalent methyne protons, and the 
corresponding 13C NMR signal is a doublet at 6 177.95 (2Jp-c 
= 11.3 Hz). The low field lH chemical shift is regarded as 
evidence for a strong ring current. The I3C NMR resonance of 
the 3a-carbon exhibits a triplet at 6 177.21 (3JpPc = 8.3 Hz). 
The 1H and 13C NMR spectra clearly imply Czv symmetry in 2a. 
The molecular structure of this unusual complex 2a is 
confirmed by an X-ray diffraction study.$ An ORTEP drawing 
of 2a is shown in Fig. 1. The coordination geometry about the 
two molybdenum atoms can be described as distorted octahe- 
dral. Two metal atoms were bridged by two phosphorus atoms 
connected by a 6a-thiathivphthen unit. The two S-S distances 
[2.318(2) and 2.330(2) A] in complex 2a are significantly 
longer than the expected S-S single bond lengths (2.05 A) but 
considerably shorter than sum of the sulfur van der Waals radii 
(3.7 A).9 Interestingly, in the crystal, 2a does not exhibit C2v 
symmetry and the P2C5H2S3 unit is not planar. To our 
Fig. 1 ORTEP drawinp for the complex [ M O ( C O ) ~ P P ~ ~ ] ~ ( ~ . - C ~ H ~ S ~ ) ,  2a. Selected bond distances (A) and angles (") are as follows: Mo(1)-P(1) 
2.528(2), Mo(2)-P(2) 2.540(2), P( 1)-C( 1 1) 1.855(4), P(2)-C( 15) 1.847(4), C( 1 1)-S( 1) 1.689(4), C( 13)-S(2) 1 .%36(4), C( 15)-S(3) 1.689(4), C( 1 1)- 
C(12) 1.352(5), C(12)-C(13) 1.415(5), C(13)-C(14) 1.399(5), C(14)-C(15) 1.371(5), S(l)-S(2) 2.318(2), S(2)-S(3) 2.330(2); C(1l)-P(1)-Mo(1) 
1 1 8, X8( 1 3), C( 15)-P(2 ~ M o ( 2 )  12 1.54( 1 3), S ( 1 )-S (2)-S( 3) 178.32(6). 
224 J. CHEM. SOC., CHEM. COMMUN., 1995 
/- 
H 
2 a M = M o  
b M = W  
3 M = Moa R = PhCH2 
4 M = W  b R = E t  \ iii l a M = M o  b M = W  
\- no reaction 
Scheme 1 Reagents and conditions: i, Et3N or Pri2NH or Et2NH or F-, 
CH2C12, 25 "C, 10 min; ii, RNH2 (R = PhCH2, Et), CH2C12, 25 "C, 
1 min; iii, BunLi or ButOK or PhNH2, THF, 25 "C, 1 h 
knowledge, complex 2a is the first example of metal-derivative 
of 6a-thiathiophthen. 
In order to study the role of Et3N in the formation of 2a, other 
amines and Bu4NF were used to replace Et3N in the reaction. 
Complexes l a  and l b  were reacted with secondary amine 
(Pri2NH, Et2NH) or Bun4NF to give 2a and 2b, respectively, 
both in high yield. The rate of formation of 2 depends on the 
amine used and decreases in the order Et3N > Pri2NH > Et2NH 
> Bun4NF. No reaction was observed when 1 was reacted with 
BunLi, ButOK or PhNH2. But the reactions of 1 with several 
primary aliphatic amines (RNH2; R = PhCH2, Et) give 
M(CO)5PPh2CSNHR (M = Mo, R = PhCH2, Et; 3a-b; M = 
W, R = PhCH2, Et; 4a-b) and HCzCCH2SH in high yield, 
Scheme 1. Interestingly, complex 3 (or 4) is not the precusor 
that leads to 2. On the basis of the above-mentioned experi- 
ments, one can conclude that secondary or tertiary amines 
catalyse the formation of 2 but primary amines or strong bases 
do not. To probe the origin of the two methyn protons of 2a 
(from the terminal or the methylene of la), 2H-labelling 
experiment was carried out. Treatment of the terminally 
labelled [2Hl]la with Et3N afforded 2a with no 2H-labelling. In 
addition, when the reaction was monitored by the 3IP and lH 
NMR spectra, complex 2a was observed as the only product 
(yield 95% from integration of the 31P NMR spectrum) and no 
intermediate was observed. Attempts to trap possible inter- 
mediates by separate addition of PPh3, CS2, TCNE, Me1 or 
cyclopentadiene into the reaction of 1 with Et3N failed to 
produce any product other than 2. The metal carbonyl fragment 
is crucial for the formation of 2, since treatment of the 
analogous organic species Et2NC(S)SCH2C-CH with Et3N or 
PhCH2NH2 resulted in no reaction under the same reaction 
conditions. In the absence of R3N, dimerization of 1 gave a five- 
membered ring consisting of a C=S unit and the propynyl 
moiety.10 
The reactivity of the 6a-thiathiophthen metal complexes and 
the mechanism for their formation are currently under in- 
vestigation. 
We thank the National Science Council of Taiwan, the 
Republic of China for support. 
Received, 2nd November 1994; Com. 4106708H 
Footnotes 
t Selected spectroscopic data: lH (300 MHz) and l3C{ lH) (75 MHz) 
NMR (298 K, CDC13, relative to SiMe4, multiplicity, assignment, J in 
Hz) 31P (121.5 MHz) NMR (H3P04 external standard). 
la: IR (CH2C12, vco/cm-I): 2075(m), 1942(vs). 3lP NMR: 6 76.76. 
'€3 NMR: 6 2.18 (t, 1H, EcH, 4 J ~ - ~  = 2.68), 3.98 (d, 2H, s-cH2, 4 J ~ - ~  
= 2.68), 7.47 (m, 6H, Ph), 7.67 (m, 4H, Ph). 13C NMR: 6 26.36 (S- 
CH2), 72.60 (KH) ,  75.77 (CECH), 128.55 (d, meta-C of Ph, 3Jp-c = 
9.60), 131.03 (s, para-C of Ph), 133.69 (d, ortho-C of Ph, 2 J p - ~  = 
11.77), 133.67 (d, ipso-C of Ph, JpPc = 30.70), 205.35 (d, CO, 2 J p - ~  = 
8.48), 209.84 (d, CS2, JPx = 26.10). MS (FAB, NBA, mlz): 539 (M+), 
[2Hl]lb (2H 98%): IR (CH2C12, vco/cm-l): 2072(m), 1940(vs). 31P 
483 (M+ - 2CO). 
NMR: 6 59.95 (Jw-p = 237.0). 'H NMR: 6 3.96 (s, 2H, S-CHz), 7.45 
(m, 6H, Ph), 7.69 (m, 4H, Ph). 
2a: IR (KBr, vco/cm-l): 2073(m), 1924(vs). 31P NMR: 6 46.59. 'H 
NMR: 6 7.41 (m, 6H, Ph), 7.52 (m, 4H, Ph), 7.90 (d, 2H, CH, 3Jp-H = 
(d, CH, 2Jp-c = 11.3), 205.22 (d, cis-CO, 2JP-c = 9.0), 209.67 (d, PCS, 
JP-,= = 24.8). MS (FAB, NBA, mlz): 1000.9 (M+), 972.9 (M+ - CO), 
2b: IR (KBr, vCo/cm-l): 2068(m), 1931(vs). 31P NMR: 6 28.54 
(JwPp = 249.6). 1H NMR: 6 7.41 (m, 6H, Ph), 7.52 (m, 4H, Ph), 7.91 
3Jp-c = 8.3), 177.30(d, CH,2JpPC = 11.3), 196.80(d,cis-CO, 2 J p - ~  = 
9.0). MS (FAB, NBA, mlz): 1176.2 (M+), 1148.0 (M+ - CO), 1064.0 
7.2). 13C NMR: 6 128-134 (Ph), 177.21 (t, HCC, 3Jp-c = 8.3), 177.95 
945 (M+ - 2CO), 916.9 (Mf - 3CO), 721.0 (M+ - lOC0). 
(d, 2H, CH, 3 J p - ~  = 8.0). '3C NMR: 6 128-134 (Ph); 177.21 (t, HCC, 
(M+ - 4CO), 1036.8 (M+ - 5CO), 1008.2 (M' - 6CO), 952.1 (M+ - 
SCO), 925.2 (M+ - SCO), 896.2 (M+ - lOC0). 
3a: 31P NMR: 6 63.47. 1H NMR: 6 4.87 (s, 2H, CH2), 7.14-7.65 (m, 
15H, Ph). MS (FAB, NBA, mlz): 571.4 (M+), 543.4 (M+ - CO). 
3.68 (9, 4H, CH2, JH-H = 7.3), 2.42 (b, lH, NH), 7.43-7.67 (m, ]OH, 
Ph) . 
4a: 31P NMR: 6 47.14 (JwPp = 256.4). lH NMR: 6 4.86 (s, 2H, 
CH2),  7.29-7.68 (m, 15H, Ph), 7.91 (d, 2H, CH, 3Jp-H = 8.0). MS 
(FAB, NBA, mlz): 659.3 (M+), 631.3 (M+ - CO). 
JHPH = 7.3), 3.95 (9, 4H, CH2, JHPH = 7.3), 7.30-7.63 (m, 10H, 
Ph) . 
$ Crystal data for 2a: C39H22010P2S3M02, space group P i ,  u = 
9.042(7), b = 15.175(6), c = 16.554(8) A, a = 112.02(4), (3 = 
96.38(4), y = 92.92(4)", V = 2082.2(21) A3, Z = 2, Dcalcd = 1.596 
g ~ m - ~ ,  p = 8.603 cm-1, observed reflections 4298, 20,,, = 45.0'. 
An absorption correction has been carried out. The structure was solved 
by Patterson synthesis then refined via standard least-squares and 
difference Fourier techniques. Non-hydrogen atoms were refined by 
using anisotropic thermal parameters. Total number of parameters: 506. 
R = 0.028,RW = 0.029; GOF = 1.36, AF = 0.51, -0.48 e A3; Atomic 
coordinates, bond lengths and angles, and thermal parameters have 
been deposited at the Cambridge Crystallographic Data Centre. See 
Information for Authors, Issue No. 1. 
3b: 31P NMR: 6 62.38. 'H NMR: 6 1.14 (t, 6H, CH3, J H - H  = 7.3), 
4b: 3'P NMR: 6 46.30 (Jw-p = 257.6). 'H NMR: 6 1.19 (t, 6H, CH3, 
References 
1 Y. Wang, S. K. Yeh, S. Y. Wu, C. T. Pai, C .  R. Lee and K. J. Lin, 
Acta Crystallogr., Sect. B: Struct. Sci., 1991,47, 298; L. K. Hansen 
and A. Hordvik, Acta. Chem. Scand., 1973,27,4 1 1 ; Q. Shen and K. 
Hedberg, J .  Am. Chem. Soc., 1974, 96, 289. 
2 R. Gleiter and R. Gygax, Top. Curr. Chem., 1976, 63, 1 .  
3 K. T. Potts, S. A. Nye and K. A. Smith, J .  Org. Chem., 1992, 57, 
3895; U. Chiacchio, A. Corsaro, A. Rescifina, M. G. Testa and G. 
Purrello, Heterocycles, 1993, 36, 223; H. G. Marei and M. M. 
Mishrikey, Phosphorus, Sulfur and Silicon, 1992, 73, 229. 
4 K. Maeda, Bull. Chem. Soc. Japan, 1961, 34, 785; R. Cimiraglia 
and H.-J. Hofmann, J .  Am. Chem. Soc., 1991, 113, 6449; A. S .  
Brown and V. H. Smith, J .  Chem. Phys., 1993, 99, 1837. 
5 H. Behringer, M. Ruff and R. Wiedenmann, Chem. Ber., 1964,97, 
1732; A. Hordvik, E. Sletten and J. Sletten, Acta Chem. Scand., 
1966, 20, 2001; R. J. S. Beer, D. Cartwright and D. Harris, 
Tetrahedron Lett., 1967, 953. 
6 R. J.  S. Beer, D. Cartwright, D. Harris and R. J. Gait, J .  Chem. Soc. 
C ,  1971, 963; G. Duguay, D. H. Reid, K. 0. Wade and R. G. 
Webster, J. Chem. SOC. C ,  1971, 2829. 
7 Y. Wang, M. J. Chen and C. H. Wu, Acta Ciystallogr., Sect. B: 
Struct. Sci., 1988, 44, 179; K. J. Lin and Y. Wang, J. Phys. Chem., 
1993, 97, 3176. 
8 K. H. Yih, Y. C. Lin, M. C. Cheng and Y. Wang, J. Chem. Soc., 
Chem. Commun., 1993, 1380. 
9 L. Pauling, The Nature of the Chemical Bond, 3rd ed., Cornell 
University Press, New York, 1960. 
10 K. H. Yih, Y. C. Lin, M. C. Cheng and Y. Wang, Organometallics, 
1994, 13, 1561. 


Synthesis and crystal structure of the first 6a-thiathiophthen metal complex [Mo(CO)_5PPh_(2]2)(µ-C_5H_2S_3)

Phosphorus, Sulfur and Silicon,

The Nature of the Chemical Bond, 3rd ed.,

http://authors.library.caltech.edu/29439/1/YIHjcscc95.pdf

Synthesis and crystal structure of the first 6a-thiathiophthen metal complex [Mo(CO)_5PPh_(2]2)(µ-C_5H_2S_3)

Abstract

Similar works

Full text

Available Versions

Caltech Authors - Main

Caltech Authors - Main