Pii: s0022-328x(97)00780-8

Journal of Organometallic Chemistry 558 (1998) 41 – 49 Synthesis and structure of methylpalladium(II) and -platinum(II) trans-PdMe(O H CH CH CH -o)(PR ) (R p2-C,C-OC H CH CH CH -o)(PMe ). Simple O-coordination and chelating coordination depending on the metal center and auxiliary Yong-Joo Kim a,*, Jae-Young Lee a, Kohtaro Osakada b a Department of Chemistry, Kangnung National Uni6ersity, Kangnung, 210-702, South Korea b Research Laboratory of Resources Utilization, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama, 226, Japan Received 8 July 1997; received in revised form 2 December 1997 Abstract
Reactions of cis-PdMe L (L = PMe , PPh , 0.5 dppp [dppp = Ph P(CH ) PPh ]) with equimolar 2-allylphenol afford the new complexes PdMe(OC H CH CH CH -o)L2 (1: L = PMe ; 2: L = PPh ; 3: L = 0.5 dppp) in moderate to high yields. Addition of
2,2,2-trifluoro-1-phenylethanol to equimolar 1 results in formation of trans-PdMe(O H CH CH CH -o)(PMe ) · (HOCH(CF )
Ph), (4) which has been characterized by X-ray crystallography and NMR spectroscopy. Complex 4 contains O – H···O hydrogen
bonding between the allylphenoxido ligand and associated alcohol (O···O = 2.635(6) A
Me(OC H CH CH CH -o)(dppp), (5) is obtained from the alkoxido ligand exchange reaction of PtMe(OCH(CF ) )(dppp) with
2-allylphenol. Similar reaction of cis-PtMe(OR)(PMe ) with equimolar 2-allylphenol at room temperature gives trans-Pt- Me(OC H CH CH CH -o)(PMe ) (6) in 55% yield. In contrast, reaction of cis-PtMe(OCH(CF ) )(PMe ) · (HOCH(CF ) ) with
excess 2-allylphenol at room temperature gives a mixture of 6 and PtMe(p1-O, p2-C,C-OC H CH CH CH -o)(PMe ) (7) which
are isolated in 16 and 28% yields, respectively. The isolated complex 7 has been characterized by NMR spectroscopy using several
pulse techniques and X-ray analysis. The molecule has a distorted square-planar coordination around the metal center. The
olefinic group in 2-allylphenoxido ligand is coordinated to the Pt center in a perpendicular fashion to the coordination plane.
1998 Elsevier Science S.A. All rights reserved.
Keywords: Palladium; Platinum; Phenoxide; Hydrogen bonding; Crystal structure 1. Introduction
the metal – phenoxido bond [9 – 11]. Most of the phe-noxido complexes were prepared by metathesis reac- The chemistry of late transition metal phenoxides has tions of chloro complex with alkaline metal phenoxido been the subject of increasing attention because of their or by reaction of hydrido or alkyl metal species with characteristic chemical properties such as C – O bond phenol. Previously we have reported that reactions of formation through coupling of the phenoxido and acyl dialkyl-nickel (II), -palladium (II), and -platinum(II) ligand [1,2], O – H···O hydrogen bonding between phe- complexes stabilized by tertiary or chelating phosphines noxido ligand and phenol [3 – 8], and CO insertion into with equimolar phenols with various substituents,HOC H X-p (X ceed smoothly at room temperature to give alkyl-nickel 0022-328X/98/$19.00 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(97)00780-8 Y.-J. Kim et al. / Journal of Organometallic Chemistry 558 (1998) 41 – 49 (II), -palladium (II), and -platinum (II) phenoxides or caused by coupling with two unequivalent phosphorus complexes, MR(OAr)L · (HOAr) containing phenol nuclei. The 1H- and 13C-NMR signals of PMe ligands associated with phenoxido ligands through hydrogen of 1 and 13C{1H}-NMR peak due to ipso carbons of
bonding [6]. Recently, van Koten and his coworkers [7] PPh ligands of 2 are observed as apparent triplets due
also showed that reactions of dimethylpalladium(II) to virtual coupling. The 13C{1H}-NMR signals due to complexes with auxiliary N,N or N,P-donor chelating olefinic carbons of 2-allylphenoxido ligand of 1 3 ap-
ligands with phenol or pare- substituted phenols lead to pear at quite similar position to each other (113.0 – the formation of palladium(II) phenoxides or those 114.0 and 139.1 – 140.0 ppm) and to the corresponding with associated phenol through the O – H···O hydrogen- signals of uncoordinated 2-allylphenol. The above re- bond stabilized by the amine ligands.
sults strongly indicate the absence of coordination or On the other hand, Pd(II) complex containing both interaction between C C double bond of the 2-allylphe- alkoxido and y-coordinated olefin ligands seems to be of importance as a possible intermediate of alkoxypal- ladation of olefins or the Wacker type reaction. A PdMe (PMe ) with excess phenol gives a complex for- strategy to isolate this kind of Pd complex and to mulated as trans-PdMe(OPh)(PMe ) · (HOPh), which investigate its properties is to use alcohol containing is prepared also from the reaction of trans-PdMe- C C double bond at the proper position to serve as the (OPh)(PMe ) with phenol [6]a. Strong O – H···O hydro- anchor in the molecule as the ligand precursor. Liga- gen bonding exists between the phenoxido ligand and tion of alkoxido would be accompanied by y-coordina- phenol not only in the solid state but in solution.
tion of the C C double bond. In this paper as an Reaction of cis-PdMe (PMe ) with excess 2-allylphe- extension of the previous work we will show chemistry nol does not produce the hydrogen-bonded complex of methylpalladium and platinum(II) complexes con- such as trans-PdMe(OC H CH CH CH -o)(PMe ) · taining 2-allylphenoxido ligand including synthetic de- (HOC H CH CH CH -o) but gives 1 as the sole
isolable product. The difference of the reaction prod- crystallographic results of some of the complexes.
ucts between phenol and 2-allylphenol is ascribed toweakening the O – H···O hydrogen bond of the 2-al-lylphenoxido ligand with 2-allylphenol caused by steric 2. Results and discussion
congestion and/or to poor crystallinity of trans-(C H CH CH CH -o)L · (HOC H CH CH CH -o), preventing from its crystallization from the solution.
dppp) with an equimolar amount of 2 allylphenol at Complex 1 reacts with equimolar 2,2,2-trifluoro-1-
0°C give trans-PdMe(OC H CH CH CH -o)L (1: L
lyl)(PMe ) · (HOCH(CF )ph) (4) as shown in Eq. (2).
o)(dppp), (3) in moderate to good yields, respectively.
Complex 4 has been isolated as a colorless crystalline
solid, and characterized by X-ray crystallography and
L − L = Ph P − (CH ) − PPh , 3
NMR spectroscopy as shown below. The structure Complexes 1 3 are colorless or yellow crystalline solids
whose IR spectra give rise to a small absorption peak at bonded to the coordinated oxygen of the 2-allylphenox- 1634 – 1636 cm−1 due to C C stretching frequency of ido ligand is stable in the solid state at room tempera- the allyl group. Similarity of the peak position to the ture but the complex readily loses the associated fluoro corresponding band of free 2-allylphenol suggests that alcohol in solution during recrystallization and regener- the C C double bond of the allylphenoxido ligand does ates complex 1.
not coordinate to the metal center. The 1H- and 13C- Fig. 1 shows the molecular structure of 4 whose
NMR spectra as well as results of 13C – 1H COSY selected bond lengths and angles are listed in Table 1.
measurement have provided sufficient information to The molecular structure of 4 contains slightly distorted
characterize these complexes unambiguously. The 1H- square planar coordination around the palladium cen- and 13C{1H}-NMR signals due to the methyl ligand of ter containing two mutually bans PMe ligands as well 1 and 2 appear at reasonable positions accompanied by
as methyl and 2-allylphenxido ligands. 2,2,2-Trifluoro- coupling with two magnetically equivalent phosphorus 1-phenylethanol forms an O – H···O hydrogen bonding nuclei. Complex 3 having cis coordination shows the
with the coordinated oxygen atom. The O···O non- 1H- and 13C{1H}-NMR signals as a doublet of doublets Y.-J. Kim et al. / Journal of Organometallic Chemistry 558 (1998) 41 – 49 The 1H-NMR spectrum of 4 taken in CDCl (25°C)
shows an OH hydrogen peak of the associated alcohol
at 5.8 ppm which is at a higher magnetic field position
than those of other palladium phenoxides with an
associated fluoro alcohol or phenol. These results indi-
cate weak hydrogen bonding between the phenoxido
and an alcohol in solution and agree with the observa-
tion that 4 dissociates easily the fluoro alcohol in the
We have examined preparation of analogous platinu- m(II) complexes. Similar reaction of PtMe (dppp) with Me(OC H CH CH CH -o)(dppp), (5) at all. On the
basis of previous our results including reaction of cis-PtMe(OCH(CF ) )(PMe ) Me(OPh)(PMe ) [6]b, similar ligand exchange reaction of cis-PtMe(OCH(CF ) )(dppp) has been carried out by Me(OC H CH CH CH -o)(dppp) (5) in 60% yield as a
Fig. 1. ORTEP drawing of 4 showing the atomic labeling scheme and
hydrogen bond with significant strength (2.55 – 2.65 A and are comparable to O···O distances and angles inrelated palladium(II) and platinum(II) alkoxide or phe-noxide complexes [4 – 7]. D-fourier technique has re-vealed position of the OH hydrogen which lies on theO – O line (O – H = 1.03(6) A The 1H-NMR spectrum of complex 5 shows the
doubles of doublets flanked with 195Pt satellite signals.
to or slightly longer than those of previously reported The 1H- and 13C{1H}-NMR signals due to the hydro- the Pd – O distances in related palladium phenoxide gens and carbons of the allyl group appear at quite complexes, bans PdMe(OC H )(PMe ) · (HOR) (R similar positions to the corresponding signals of the Pd complex 3. The 31P{1H}-NMR spectrum of 5 shows
two doublets which are accompanied by 195Pt satellites in agreement with the cis configuration having unequiv- ers have observed similar slight elongation of the Pd – O alent phosphine ligands. The signal at 7.73 ppm with bond of phenoxido complex with chelating diamine coupling constant, J(195Pt – 31P) = 1546 Hz, is assigned auxiliary ligands [7]a,c. Non-bonded distance between to the phosphorus atom at the trans position to the Pd and hydrogen bonded to C17 of the fluoro alcohol methyl ligand, while the other phosphorus nuclei bans in 4 (2.73 A
˚ ) falls within the expected sum of van der to the 2-allylphenoxido ligand shows a much larger Waals radii of H and 4d group metals, indicating the coupling constant, J(195Pt – 31P) = 3807 Hz, similarly to presence of agostic interaction between the C – H group the already reported cis methylplatinum alkoxido com- plexes, cis-PtMe(OPh)(PMe ) [6]b, PtMe(OMe)(dppe) [13], and related Pt complexes [14].
Use of monodentate coordinating PMe as the auxil- ˚ ) and angles (°) for 4
iary ligands have altered the products of the reaction of the fluoroalkoxido platinum complexes with 2-allylphe- nol. Reaction of cis-PtMe(OCH(CF ) )(PMe ) equimolar 2-allylphenol at room temperature gives trans-PtMe(OC H CH CH CH -o)(PMe ) , (6) in a
55% yield as shown in Eq. (4). However, similar reac- tion of cis-PtMe(OCH(CF ) )(PMe ) · (HOCH(CF ) ) with excess 2-allylphenol at room temperature results in formation of a mixture of 6 and Pt-Me(OC H CH CH
Y.-J. Kim et al. / Journal of Organometallic Chemistry 558 (1998) 41 – 49 CH -o)(PMe ) (7) which are isolated by fractional
recrystallization of the product in the respective yieldsof 16% and 28% as shown in Eq. (5).
The IR spectrum of 6 shows the presence of the
alkenyl stretching vibration (w(C C)) in the phenoxido
ligand at 1636 cm−1 similarly to 1 3 (1636 – 1634 cm−
1), while the corresponding peak of 7 is shifted to lower
frequency region (1600 cm−1) by y-coordination to the
Pt center. The 1H spectrum of 6 at − 20°C shows the
Fig. 2. ORTEP drawing of 7 showing the atomic labeling scheme and
signal due to Pt – CH hydrogen as a triplet flanked with 195Pt satellites. The PMe hydrogen signal observed as an apparent triplet due to virtual coupling is also distorted square planar coordination around the Pt accompanied by 195Pt satellites. The other signals in- center which is bonded to a PMe , a methyl, and a cluding allyl hydrogen peaks of the 2-allylphenoxido 2-allylphenoxido group whose C C double bond is ligand are observed quite similarly to the bans Pd coordinated to the metal center. The C2 – C1 bond in complex 1. The 31P{1H}-NMR signal of 6 shows the
2-allylphenoxido ligand is perpendicularly coordinated 31P–195Pt coupling (2667 Hz) which is similar to the to the coordination plane with almost equal Pt – C bond already reported monomethyl complexes of Pt(II). In distances (Pt – C1 = 2.13 and Pt – C2 = 2.16 A contrast, the Pt – Me signal in 1H- spectrum of 7 ex-
C2 – C1 bond length of 7 is 1.32 A
hibits a doublet (J(PH) = 3 Hz) with 195Pt satellites due to the structure having the methyl and PMe ligands at mutually cis positions. The 13C{1H}-NMR signals due to olefinic carbons of the 2-allylphenoxido ligand are observed at 79.2 and 97.8 ppm which are significantly y-back donation of metal to olefin and vice verse at higher magnetic field position than the correspond- electron drift of olefin to metal is significant in 7. The
ing peaks of other Pd and Pt complexes in the present ˚ ) of 7 is shorter than
study and those of 2-allylphenol. 195Pt satellite peaks those of cis-PtMe(OCH(CF ) )(PMe ) (2.13(2) A are clearly observed, indicating that the C C double bond is firmly y-coordinated to the metal center. The suggest the C C double bond has much weaker trans 1H NMR signals corresponding to, CH , CH–, and – CH – hydrogens of the 2-allylphenoxido ligand also shows splitting due to 195Pt – 1H coupling and upfield shift of the peak positions compared with those of 6 ˚ ) and angles (°) for 7
whose C C double bond is not bonded to the Pt center.
Assignment of these 1H and 13C signals are confirmed with the aid of 13C – 1H COSY measurement and the 13C-NMR spectrum obtained in a gated decoupled mode. In order to obtain more precise structural infor- mation we have undertaken the study on the crystal A suitable crystal of 7 for X-ray analysis was ob-
tained by recrystallization from a THF hexane mixture.
Fig. 2 shows the molecular structure with the atomic numbering scheme. Selected data of bond lengths and angles are listed in Table 2. The molecule has slightly Y.-J. Kim et al. / Journal of Organometallic Chemistry 558 (1998) 41 – 49 In order to obtain more detailed insight for forma- recorded on a Hitachi 270-30 spectrophotometer. NMR tion of 7 in the reaction (5) we have examined the
(1H, 13C{1H} and 31P{1H}) spectra were obtained on reaction of isolated complex 6 with excess 2-allylphenol
JEOLFX-100, GX-270 and Braker 500 MHz spectrom- but observed complete recovery of the starting material.
eters. Chemical shifts were referred to internal Me Si or Warming a CDCl solution of 6 at
temperature leads to partial conversion of the complex PdMe (dppp) was obtained from ligand substitution into cis-isomer and ensuing formation of uncharacter- reaction of PdMe (tmeda) [21] with equimolar dppp ized complexes in trace amounts. These results exclude (90%). 1H-NMR(200 MHz, CDCl , 6): 0.16(bd, 6H, a simple pathway from 6 to 7 involving the cis isomer
CH ), 1.85 (m, 2H, – CH ), 2.4 (m, 4H, P – CH ), 7.4 – of 6 as the intermediate. However, reaction of cis-Pt-
7.7 (m, 20H, aromatic). 31P-NMR (40 MHz, CDCl , b): Me(OCH(CF ) )(PEt ) with 2-allylphenol results in the 6.3 (s). Anal. Calcd for C H P Pd: C, 63.46; H, 5.88.
o)(PEt ) (8) which is isolated in 48% yield. At present
formation mechanism of 7 in the reaction system is not
3.2. Preparation of trans-PdMe(OC H CH CH CH -o)L (1: L
; 2: L
; 3 L
In summary, the attempts to synthesize methylpalla- dium(II) or -platinum(II) complexes with 2-allylphenox- To an Et O (10 ml) solution of cis-PdMe (PMe ) (562 mg, 1.95 mmol) was added 2-allylphenol (309 mg, allylphenoxido group is bonded in a simple O-bonded 2.30 mmol) at 0°C. After stirring the reaction mixture fashion. These complexes do not show coordination or for 6 h the solvent was reduced under vacuum to cause interaction of the C C double bond of the ligand to the separation of colorless crystals, which were recrystal- fifth coordination site of the metal center. Ligand ex- lized from ether to give 1 (475 mg, 62%). IR (KBr):
change reaction of the methylplatinum fluoroalkoxido 1636 cm−1 (w(C C)). 1H-NMR (CDCl , 500 MHz, l): complex by 2-allylphenol resulted in formation of the 0.02 (t, 3H, J = 7 Hz, Pd – CH ), 1.25 (t, 18H, J square-planar complex as one of the products, which possesses the phenoxido ligand containing C C double (dd, 1H, J = 10, 2 Hz, – CH CH CH ), 5.02 (dd, 1H, bond y-coordinated to the metal center. The bond parameters of the olefinic group bonded to the Pt CH CH CH ), 6.4 (m, 1H, aromatic), 6.93 (m, 2H, center suggests back donation in almost negligible de- aromatic), 7.05 (m, 1H, aromatic). 13C{1H} NMR (125 gree. Chelating complexation of the 2-allylphenoxido MHz, CDCl , l): −12.7 (t, J=7 Hz, Pd–CH ), 13.1 ligand in 7 despite selective formation of simple O-co-
ordinated phenoxides in the reactions of dimethylpalla- CH CH CH ), 139.1 ( – CH CH CH ), 111.5, 118.5, dium complexes can be partly attributed to more labile 126.7, 128.4, 129.2, 167.9 (aromatic). 31P{1H}-NMR Pd – PMe bond than the Pt – PMe bond.
C H OP Pd: C, 47.24; H, 7.43. Found: C, 47.30; 3. Experimental
trans-PdMe(OC H CH CH CH -o)(PPh ) , (2) and
3.1. General, materials, and measurement PdMe(OC H CH CH CH -o)(dppp), (3) were similarly
obtained in 85 and 86% yields. Complex 2. IR (KBr):
All manipulations of air-sensitive compounds were 1634 cm−1 (w(C C)). 1H-NMR (CDCl , 500 MHz, 6): performed under N or argon atmosphere with use of 0.07 (bs, 3H, Pd – CH ), 2.80 (d, 2H, J standard Schlenk technique. Solvents were distilled CH CH CH ), 4.85 (m, 2H, – CH CH CH ), 5.77 (m, from Nabenzophenone. dppp (1,3-bis(diphenylphos- phino)propane), PMe , PPh , 2-allylphenol, 2,2,2-trifl- C{1H}-NMR (125 MHz, CDCl , l): −1.92 (s, Pd– CH ), 35.1 ( – CH CH CH ), 113.2 ( – CH CH CH ), propanol were purchased from Aldrich and used with- 139.5 ( – CH CH CH ), 110.6, 119.4, 125.6, 126.8, out further purification. cis-PdMe L (L 128.1, 129.9. 130.3, 131.4, 134.6, 166.5 (aromatic).
31P{1H}-NMR (200 MHz, CDCl , l): 26.8 (s). Anal.
Me(OCH(CF ) )(PMe ) · (HOCH(CF ) [6]b, and Pt- Calcd for C H OP Pd: C, 70.91; H, 5.43. Found: C, Me(OCH(CF ) )(dppp) [20] were prepared by the Complex 3. IR (KBr): 1634 cm−1 (w(C C)). 1H-
Elemental analyses were carried out by the analytical NMR (CDCl , 500 MHz, l): 0.32 (dd, 3H, J laboratory, Tokyo Institute of Technology in Japan Pd – CH ), 1.86 (m, 2H, P – CH ), 2.43 (m, 4H, P – CH ), and Basic Science Institute of Korea. IR spectra were 3.03 (d, 2H, J = 5 Hz, – CH CH CH ), 4.80 (dd, 1H, Y.-J. Kim et al. / Journal of Organometallic Chemistry 558 (1998) 41 – 49 J = 10.2 Hz, – CH CH CH ), 4.89 (dd, 1H, J J(PtH) = 54 Hz, Pt – CH ), 1.91 (m, 2H, P – CH ), 2.48 – Hz, – CH CH CH ), 5.86 (m, 1H, – CH CH CH ), 2.55 (m, 4H, P – CH ), 2.98 (d, 2H, J = 7 Hz, – 6.23 (m, 1H, aromatic), 6.77 (m, 2H, aromatic), 7.14 – 7.96 (m, 1H, aromatic). 13C{1H}-NMR (125 MHz, CH CH CH ), 5.77 (m, 1H, – CH CH CH ), 6.36 (m, J = 6, P – CH ), 27.2 (dd, J aromatic), 6.78 – 7.69 (m, aromatic). 13C{1H}-NMR (dd, J = 8.30 Hz, P – CH ), 35.7 ( – CH CH CH ), 113.0 19.6 (d, J = 2 Hz, P – CH ), 26.7 (d, J Anal. Calcd for C H OP Pd: C, 66.62; H, 5.74.
( – CH CH CH ). 31P{1H}-NMR (200 MHz, CDCl , l): 0.06, 7.73 (d, J=20 Hz, J(PtP)=3807, 1546 Hz).
3.3. Preparation of trans-PdMe(OC H CH CH Anal. Calcd for C H OP Pt: C, 58.80; H, 5.07.
CH -o)(PMe ) · (HOCH(CF )Ph) (4)
3.5. Preparation of trans-PtMe(OC H CH CH CH -o)(PMe ) , (6) and PtMe(OC H CH CH
mmol) was added 2,2,2-trifluoro-1-phenylethanol (142 CH -o)(PMe ), (7)
mg, 0.81 mmol) at room temperature. After stirring thereaction mixture for 2 h the solvent was evaporated to dryness to leave a pasty material. Addition of hexane (5 ml) and ensuing storage of the resulting solution added 2-allylphenol (80 mg, 0.598 mmol) at room overnight at − 20°C caused separation of 4 as a color-
temperature. Stirring the reaction mixture for 4 h less crystals which were collected by filtration, washed caused separation of a white solid which was filtered, with hexane, and dried in vacuo (338 mg, 83%). IR washed with hexane, and dried in vacuo to give 6 (136
(KBr): 1636 cm−1 (w(C C)). 1H-NMR (CDCl , 500 mg, 55%). IR (KBr): 1636 cm−1 (w(C C)). 1H-NMR MHz, l): 0.08 (t, 3H, J=7 Hz, Pd–CH ), 1.20 (t, 18H, (CDCl , 500 MHz, l): 0.27 (t, 3H, J=7 Hz, J(PtH)= J = 3 Hz, P(CH ) ), 3.38 (d, 2H, J 79 Hz, Pt – CH ), 1.33 (t, 18H, J = 3 Hz, J(PtH) = 27 Hz, P(CH ) ), 3.35 (d, 2H, J = 5 Hz, – CH CH CH ), 4.98 (dd, 1H, J = 10.2 Hz, – CH CH CH ), 5.02 (dd, – CH CH CH ), 5.30 (q, 1H, J 1H, J = 17.2 Hz, – CH CH CH ), 6.07 (m, 1H, – 5.80 (bs, 1H, – OH), 6.05 (m, 1H, – CH CH CH ), 6.45 CH CH CH ), 6.43 (m, 1H, aromatic), 6.98 (m, 2H, (m, 1H, aromatic), 6.97 (m, 2H, aromatic), 7.12 (m, 1H, aromatic), 7.33 (m, 1H, aromatic). 13C{1H}-NMR (125 aromatic), 7.40 (m, 4H, aromatic), 7.56 (m, 1H, aro- MHz, CDCl , l): −29.9 (t, J=6 Hz, Pt–CH ), 12.2 ) ), 35.6 (s, – CH CH CH ), 113.7 (t, J = 7 Hz, Pd – CH ), 12.9 (t, P(CH ) ), 35.0 ( – ( – CH CH CH ), 139.2 ( – CH CH CH ), 111.8, 117.5, CH CH CH ), 138.8 ( – CH CH CH ), 112.9, 118.7, 126.6, 128.4, 129.3, 168.0 (aromatic). 31P{1H}-NMR 123.8, 126.1, 126.7, 127.8, 128.3, 128.9, 136.2, 167.9 − 7.79 (s, J(PtP) = 2667 Hz).
(aromatic). 31P{1H}-NMR (200 MHz, CDCl , l): Anal Calcd for C H OP Pt: C, 38.79; H, 6.10. Found 13.6 (s). Anal. Calcd for C H F O P Pd: C, 49.45; H, To an ether solution (10 ml) containing cis-Pt- 3.4. Preparation of PtMe(OC H CH CH 1.01 mmol) was added 2-allylphenol (0.284 g, 2.12 CH -o)(dppp), (5)
mmol) at room temperature. After stirring the reaction mixture for 4 h the solvent was evaporated to dryness to leave a pasty material. Addition of hexane (7 ml) and Me(OCH(CF ) )(dppp) (273 mg, 0.35 mmol) was added ensuing storage of the resulting solution at − 70°C for 2-allylphenol (59 mg, 0.7 mmol) at room temperature.
overnight caused separation of a colorless solid, white Stirring the reaction mixture for 4 h caused separation was collected by filtration, and washed with hexane (2 of a white solid which was collected by filtration, ml × 2), ether (3 ml × 2) at 0°C to afford 7 (118 mg,
washed with hexane, and dried in vacuo to give 5 (156 28%). IR (KBr): 1600 cm−1 (w(C C)). 1H-NMR mg, 60%). IR (KBr): 1636 cm−1 (w(C C)). 1H-NMR (CDCl , 500 MHz, l): 1.05 (d, 3H, J (CDCl , 500 MHz, l): 0.43 (dd, 3H, J 68 Hz, Pt – CH ), 1.53 (bd, 9H, J Y.-J. Kim et al. / Journal of Organometallic Chemistry 558 (1998) 41 – 49 Hz, P(CH ) ), 3.18 (d, 1H, J 3.31 (d, 1H, J = 15 Hz, – CH CH CH ), 4.00 (bd, Crystallographic Data for 4 and 7
2H, – CH CH CH ), 5.05 (m, 1H, – CH CH CH ), 6.54 (m, 1H, aromatic), 6.83 (m, 1H, aromatic), 6.91(m, 1H, aromatic), 7.12 (m, aromatic). 13C{1H}-NMR 13.9 (d, J = 43 Hz, J(PtC) = 43 Hz, P(CH ) ), 35.2 (s, J(PtC) = 23 Hz, – CH CH CH ), 79.2 (s, J(PtC) – CH CH CH ), 97.8 (s, J(PtC) CH CH CH ), 115.2, 120.3, 121.8, 128.9, 130.3, 162.6 (aromatic). 31P{1H}-NMR (200 MHz, CDCl , l): 29.6 (s, J(PtP) = 3826 Hz). Anal. Calcd for C H OPPt: C, 37.23; H, 5.06. Found: C, 37.25; H, 5.09.
Cooling the filtrate obtained by separation of 7 at
− 70°C caused separation of complex 6 as a colorless
3.6. Preparation of cis-PtMe(OC H CH CH CH -o)(PEt ) , (8)
1,1,1,3,3,3-hexafluoro-2-propanol (83 mg, 0.49 mmol) R = SF F )/S F , Rw = [Sw( F F )2/Sw(F )2]1/2 at room temperature. After stirring the reaction mix- ture for 6 h the solvent was evaporated to dryness toleave a colorless oily material. It was dissolved in an phy were obtained by recrystallization from Et O-hex- ether (5 ml) solution of 2-allylphenol (66 mg, 0.498 ane and THF-hexane mixtures, respectively, and mmol). Stirring the solution was continued for 12 h at mounted in glass capillary tubes under argon. The unit room temperature, and then the solvent was fully cell parameters were obtained by least-squares refine- evaporated to give an oily material. Addition of hex- ment of setting angles of 20 reflections with 20 52q5 ane (5 ml) to the product and ensuing storage of the 30°. Intensities were collected on a Rigaku AFC-SR resulting solution at − 20°C overnight caused separa- automated four-cycle diffractometer by using Mo-K tion of a white solid which was collected by filtration and washed with hexane (3 ml × 2) to give 8 (0.138 g,
culations were carried out by using a program package 48%). IR (KBr): 1634 cm−1 (w(C C)). 1H-NMR TEXSAN on a DEC Micro VAXII computer. A full (CDCl , 500 MHz, l): 0.51 (dd, 3H, J matrix least-squares refinement was carried out by ap- J(PtH) = 49 Hz, Pt – CH ), 1.16 (m, 9H, P(CH CH ) ), plying anisotropic thermal factors to all the non-hy- 1.80 (m, 6H, P(CH CH ) ), 3.48 (d, 2H, J drogen atoms. Hydrogen atoms were located from calculation by assuming the ideal positions (d(C – H) = CH CH CH ), 6.12 (m, 1H, – CH CH CH ), 6.50 (m, ˚ ) and included the structure calculation without aromatic), 7.00 (m, aromatic). 13C{1H}-NMR (125 further refinement of the parameters. Absorption cor- rection by „ scan method of the collected data was (d, P(CH CH ) ), 15.1 (d, J applied. Crystallographic data and atomic coordinates 16.7 (d, J = 3, J(PtC) = 40 Hz, P(CH CH ) ), 34.9 (s, of the non-hydrogen atoms are listed in Tables 3 – 5.
CH CH CH ), 113.9 ( – CH CH CH ), 139.6 ( – Hydrogen atoms of 4 were located by calculation as-
CH CH CH ), 112.7, 119.5, 126.1, 128.1, 130.1, 165.8.
suming the ideal geometry (d(CH) = 0.95 A 31P{1H}-NMR (200 MHz, CDCl , l): 2.79, 22.3 (d, throughout the structural calculation except for the J = 10 Hz, J(PtP) = 3869, 1722 Hz). Anal. Calcd for OH hydrogen which was located in final D-map and C H OP Pt: C, 45.59; H, 7.30. Found: C, 45.56; H, refined isotropically. Hydrogen atoms of 7 were lo-
cated by calculation. C1, C2 and C13 were refinedisotropically, whereas the other non-hydrogen atoms 3.7. X-ray structure determination were refined anisotropically. Insufficient convergence
of the structural calculation of 7 is due to the an-
Crystals of 4 and 7 suitable for X-ray crystallogra-
isotropic shape of the crystal with a large absorption Y.-J. Kim et al. / Journal of Organometallic Chemistry 558 (1998) 41 – 49 Acknowledgements
Atomic coordinates and isotropic temperature factors for 4
This work was supported by the agreement program of Japan Society for the Promotion of Science (JSPS) and the Korea Science and Engineering Foundation (1995) and partly by the Basic Science Research Insti- tute Program (No. BSRI-96-3440), Korean Ministry of Education. We are grateful to Dr. Masako Tanaka and Mr. Jun-Chul Choi of Tokyo Institute of Technology in References
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