Synthesis of hydridoplatinum-molybdenum (or tungsten) heterodinuclear complexes by β-hydrogen elimination of (dppe)EtPt-MCp(CO)3. Selective hydride transfer from Pt to Mo (or W)

DOI: 10.1016/S1381-1169(00)00171-0

Source and publish data:

Journal of Molecular Catalysis A: Chemical p. 63 - 70 (2000)

Update date:2022-09-26

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Authors:

Komiya, Sanshiro

Yasuda, Toshiyuki

Fukuoka, Atsushi

Hirano, Masafumi

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Article abstract of DOI:10.1016/S1381-1169(00)00171-0

Hydridoplatinum-molybdenum (or tungsten) heterodinuclear complexes (dppe)HPt-MCp(CO)₃ [M = Mo (1), W (2); dppe = 1,2-bis(diphenylphosphino)ethane] have been prepared by selective β-hydrogen elimination of corresponding ethylplatinum-molybdenum

Full text of DOI:10.1016/S1381-1169(00)00171-0

Journal of Molecular Catalysis A: Chemical 159 2000 63–70

www.elsevier.comrlocatermolcata

Synthesis of hydridoplatinum–molybdenum or tungsten

heterodinuclear complexes by b-hydrogen elimination of

ž /

dppe EtPt–MCp CO . Selective hydride transfer from Pt to

Mo or W

Sanshiro Komiya⁾, Toshiyuki Yasuda, Atsushi Fukuoka, Masafumi Hirano

Department of Applied Chemistry, Faculty of Technology, Tokyo UniÕersity of Agriculture and Technology, 2-24-16 Nakacho, Koganei,

Tokyo 184-8588, Japan

Abstract

Ž .

dppes1,2-bis diphenylphosphino ethane have been prepared by selective b-hydrogen elimination of corresponding eth-

. w Ž . Ž .x

Hydridoplatinum–molybdenum or tungsten heterodinuclear complexes dppe HPt–MCp CO MsMo 1 , W 2 ;

ylplatinum–molybdenum or tungsten complexes dppe EtPt–MCp CO MsMo 3 , W 4 . The b-hydrogen elimination

process is significantly facilitated by electron-withdrawing transition metal ligand at platinum such as Co CO

Ž .

5 .

Acetylenes having electron withdrawing groups induce selective hydride transfer reaction in these heterodunucelar complex

1–2 to give hydridomolybdenum or tungsten and zero-valent acetylene platinum complexes. q 2000 Elsevier Science

Keywords: Heterodinuclear complexes; b-hydrogen elimination; Hydride transfer; Kinetics; Platinum

1. Introduction

Combination of two or more different metals in

catalysis is especially interesting, since industri-

ally important catalyses such as Pt–Re naphtha

reforming catalyst and Co–Mo or Ni–Mo hy-

drodesulfurization catalysts are achieved by the

bimetallic catalysts, probably for the sake of

cooperative effects of two metals. In order to

obtain fundamental insight concerning such ef-

fects, we have prepared a series of heterodinu-

clear organometallic complexes having both di-

Cooperative effect in multimetallic catalysis

is one of the most intriguing and interesting

unsolved problems at the molecular level both

in homo- and heterogeneous catalyses 1–11 .

)

Corresponding author. Tel.: q81-42-387-7500; fax: q81-42-

rect M–R and M–M^Xs-bonds, L_nRM–M^XL_m

387-7500.

MsPt, Pd, Ni, Au; M sMo, W, Co, Fe, Re;

E-mail address: komiya@cc.tuat.ac.jp S. Komiya .

PII: S1381-1169 00 00171-0

(

)

S. Komiya et al.rJournal of Molecular Catalysis A: Chemical 159 2000 63–70

Ž . Ž . w Ž .

plexes dppe EtPt–MCp CO MsMo 3 , W

Lscod, dppe, bpy, PPh₃; L sCp, CO as

Ž .x

possible models in bimetallic catalyses 12–18 .

4 at 808C for 6 h. In these reactions, equimo-

lar amounts of ethylene along with small

amounts of ethane were liberated by b-hydro-

gen elimination. The total yields of ethane for

( )

Ž .

dppe EtPt–WCp CO

2 , dppe EtPt–

Ž .

Co CO 5 , and PtEtCl dppe were 3%, 14%

and 5% yields, respectively, which would be

formed by the bimolecular reaction of ethylplat-

inum with hydridoplatinum complexes. These

dinucelar complexes were characterized by IR

and NMR spectroscopies and elemental analy-

ses as well as by chemical reactions. On the

Ž .

In this paper we report preparation of hydri-

doplatinum–tungsten and –molybdenum het-

other hand, thermolysis of dppe EtPt–Co CO

erodinuclear complexes dppe HPt–MCp CO

also liberated ethylene as a major gaseous prod-

uct, though the platinum products were not iso-

lated in pure form. Table 1 summarizes yields,

melting points, molar electric conductivities in

THF, and analytical data for these hydridoplat-

by thermal b-hydrogen elimination of dppe -

Et–MCp CO and hydride transfer from Pt to

group 6 metals induced by acetylene com-

pounds. A part of the results has been reported

as a preliminary form 16 .

inum–Mo or W complexes with bidentate

phosphine ligand. IR and H and P H NMR

data for these complexes are summarized in

Table 2.

2. Results and discussion

dppe EtPtyMCp CO

2.1. Preparation of hydridoplatinum –

molybdenum and –tungsten heterodinuclear

complexes

808C

dppe HPtyMCp CO qC H

CH ₂Ph₂

MsMo 1 W 2

Ž .

Ž . Ž .

Hydridoplatinum–molybdenum and –tungs-

ten heterodinuclear complexes dppe HPt–

IR spectra of these complexes display y Pt–

MCp CO

dppes1,2-bis diphenylphoshpino

H bands at ca. 2020–2050 cm

and y CO

bands at 1788–1924 cm^y¹. H NMR spectrum

Ž .

Ž .x

ethane: MsMo 1 , W 2 have been prepared

by thermolysis of ethylplatinum–metal com-

of 1 and 2 show a doublet of doublets with ¹⁹⁵Pt

Table 1

Yields, melting points, molar electric conductivities, and analytical data for 1–5

Complex

Yield, %

M.p.,^a8CP

L,^bS cm²mol^y1

Anal., %

Calcd.

Found

Calcd.

Found

. Ž .

dppe HPt–MoCp CO

188 dec.

0.080

–

0.027

0.039

0.13

48.64

43.89

49.84

45.25

48.43

48.99

44.03

50.09

43.97

47.49

3.60

3.15

3.95

3.59

3.68

3.67

3.26

4.44

4.37

3.73

. Ž .

dppe HPt–WCp CO

211 dec.

. Ž .

dppe EtPt–MoCp CO

141 dec.

. Ž .

dppe EtPt–WCp CO

157 dec.

. Ž³.

dppe EtPt–Co CO

154 dec.

^aMelting points were uncorrected.

^bIn THF at 208C.

(

)

S. Komiya et al.rJournal of Molecular Catalysis A: Chemical 159 2000 63–70

Table 2

IR, ¹H-,

Ä¹

H -NMR data for 1–5

Ä¹

Ž .

Complex

IR^acm

H NMR^b

H NMR d

49.76 d, J_{P – Pt}s3.7 Hz,

dppe HPt–Mo

. Ž .

2050

y2.37 d, 1H, J_{H – P}s194 Hz, J_{H – Pt}s868 Hz, PtH

J_{P – Pt}s3313 Hz

Cp CO

51.58 d, J_{P – Pt}s3.7 Hz,

1926

1.7–2.0 m, 4H, PC H₂C H₂P

J_{P – Pt}s2113 Hz

Ž .

5.27 s, 5H, Cp

6.9–7.2 m, 12H, m-, p-Ph

1831

1818

7.6–7.8 m, 8H, o-Ph

51.29 d, J_{P – Pt}s4.9 Hz,

dppe HPt–W-

. Ž .

2042

1923

y2.92 d, 1H, J_{H – P}s193 Hz, J_{H – Pt}s892 Hz, PtH

J_{P – Pt}s3226 Hz

Cp CO

51.58 d, J_{P – Pt}s4.9 Hz,

1.8–1.9 m, 4H, PC H₂C H₂P

J_{P – Pt}s2090 Hz

Ž .

5.21 s, 5H, Cp

1831

1812

6.9–7.2 m, 12H, m-, p-Ph

7.6–7.8 m, 8H, o-Ph

dppe EtPt–Mo-

. Ž .

1902

1788

0.72 dtd, 3H, J_{H – P}s11, J_{H – H}s7.5,

39.58 s, J_{P – Pt}s1508 Hz

Cp CO

J_{H – P}s1.8 Hz, J_{H – Pt}s40 Hz, PtCH₂C H₃

59.47 s, J_{P – Pt}s3711 Hz

1.51 dqd, 2H, J_{H – P}s7.5,

J_{H – H}s7.5, J_{H – P}s7.5 Hz, J_{H – Pt}s63 Hz, PtC H₂CH₃

2.0–2.3 m, 4H, PC H₂C H₂P

4.65 s, 5H, Cp

7.5–7.6 m, 12H, m-, p-Ph

7.7–8.0 m, 8H, o-Ph

dppe EtPt–W-

. Ž .

1899

1789

0.71 dtd, 3H, J_{H – P}s11, J_{H – H}s7.2,

40.14 s, J_{P – Pt}s1502 Hz

Cp CO

J_{H – P}s1.5 Hz, J_{H – Pt}s42 Hz, PtCH₂C H₃

1.66 dqd, 2H, J_{H – P}s7.2, J_{H – H}s7.2,

61.11 s, J_{P – Pt}s3677 Hz

J_{H – P}s7.2 Hz, J_{H – Pt}s77 Hz, PtC H₂CH₃

2.0–2.3 m, 4H, PC H₂C H₂P

4.70 s, 5H, Cp

7.4–7.6 m, 12H, m-, p-Ph

7.7–8.0 m, 8H, o-Ph

dppe EtPt–Co-

. Ž .

2024

1957

0.74 dt, 3H, J_{H – P}s9.4 Hz, J_{H – H}s8.1 Hz,

47.76 s, J_{P – Pt}s2797 Hz

J_{H – Pt}s35 Hz, PtCH₂C H₃

47.95 s, J_{P – Pt}s4096 Hz

1.48 dqd, 2H, J_{H – P}s8.1, J_{H – H}s8.1,

J_{H – P}s8.1Hz,

J_{H – Pt}s45 Hz, PtC H₂CH₃

Ž .

1924

1883

2.1–2.5 m, 4H, PC H₂C H₂P

7.4–7.6 m, 12H, m-, p-Ph

7.6–7.9 m, 8H, o-Ph

^aKBr disk.

^b300 MHz, in C₆D₆for 1–4, in CD₂Cl₂for 5.

^c122 MHz, in C₆D₆for 1–4, in CD₂Cl₂for 5.

satellite for the hydride. While the hydride has a

2.2. Thermal b-hydrogen elimination of eth-

ylplatinum–molybdenum and –tungsten het-

erodinuclear complexes

large coupling constant to trans-P nucleus 194

Hz for 1, 193 Hz for 2 , negligible coupling

constant to cis-P is observed, suggesting dis-

tinct difference of trans influence in the square

Time-courses of thermal b-hydrogen elimina-

tion reactions of these heterodinuclear com-

plexes were followed in diphenylmethane at

808C by monitoring the evolved ethylene by

GLC. Fig. 1 shows the linear relationship be-

planar configuration. ³¹P H NMR displays two

doublets with Pt satellites J_{P – P}s3.7–4.9 Hz,

J_{P – Pt}s2090–3313 Hz , the small J_{P – P}values

also being consistent with the square planar cis

x_t4.

structure of these complexes.

tween

ethylene r ethylene _`y ethylene

(

)

S. Komiya et al.rJournal of Molecular Catalysis A: Chemical 159 2000 63–70

trans-PtEtCl PPh_{3 2}is reported to form trans-

w x

PtHCl PPh_{3 2}by thermolysis 19 . The b-hy-

drogen elimination reaction in EtPt–Co com-

plex 5 was the fastest, followed by EtPt–Mo

Ž .

3 , EtPt–W 4 and the monomeric EtPt–Cl

complexes. This trend may be interpreted by

enhanced electrophilicity at Pt metal center due

to more electronegative transition metal such as

tetracarbonylcobalt ligand, giving rise to a facile

hydrogen elimination. Eyling plot 76–918C of

the first order rate constants for the thermolysis

of 3 gave kinetic parameters D H ^/s100"2

kJrmol, DS^/sy26"4 kJrmolrK and DG^/

818C s110"4 kJrmol Fig. 2 . The negative

value of entropy of activation suggests that the

reaction does not involve dissociative processes

such as prior dissociation of dppe or Mo anion

ligands, as frequently observed in thermolysis

of such organotransition metal complexes. Prob-

ably the b-hydrogen elimination has a relatively

restricted environment where the b-hydrogen

has an interaction with Pt by using the fifth

coordination site of square planar geometry at

Fig. 1. First order rate plots for the thermolysis of dppe EtPt–

. Ž . Ž . Ž . Ž

MoCp CO 3 , dppe EtPt–WCp CO 4 , dppe EtPt–Co CO

Ž .

5 , and PtEtCl dppe at 808C in diphenylmethane.

and time, indicating that the reactions are first

order in the concentration of heterodinuclear

complexes under these conditions. The reactions

can also be followed by monitoring the forma-

tion of the dinuclear hydride complexes in

toluene-d₈to give approximately the same rate

constants. These results indicate that the ther-

molysis of these complexes gave concomitant

formation of ethylene and dinuclear hydride

complex. Estimated first order rate constants for

these reactions are summarized in Table 3.

Pt Scheme 1 20–23 .

Hoffmann et al. proposed that the reaction of

ethylene with PtHCl PH_{3 2}, the reverse reaction

of b-hydrogen elimination, undergoes via a

cationic 3-centered intermediate by the prior

dissociation of chloride anion 24 . However,

possible prior heterolytic dissociation of Mo

anion is excluded, because no additive effect of

d dppe EtPtyMCp CO

d dppe HPtyMCp CO

Table 3

Ž .

First order rate constants for b-hydride elimination of dppe EtPt–

ML_n

d CH₂sCH₂

Complex

_obs=10⁴, s^y1

dppe EtPt–MoCp CO

4.0^a,b

2.8^a,b

3.7^c

2.7^c

–

. Ž .

dppe EtPt–WCp CO 4

. Ž³.

sk_obsddppe EtPtyMCp CO

12^a,b

dppe EtPt–Co CO

PtEtCl dppe

0.78^a,b

–

For comparison, the first order plots for the

thermolysis of monomeric platinum complex

PtEtCl dppe are also shown in Fig. 1. Although

the fate of the platinum moiety by thermolysis

of PtEtCl dppe is not clear, PtHCl dppe is the

most likely product because the related complex

^aEstimated from formation of ethylene by GLC in CH₂Ph₂at

808C.

^bStandard deviations are as follows: 0.1 for 3, 0.1 for 4, 2 for

5 and 0.03 for PtEtCl dppe .

^cEstimated from formation of dppe HPt–ML_nby NMR in

C₆D₅CD₃at 808C.

(

)

S. Komiya et al.rJournal of Molecular Catalysis A: Chemical 159 2000 63–70

considered to prevent the phosphine dissociation

process, and therefore electron withdrawing

transition metal consequently enhances the di-

rect b-hydrogen elimination process at Pt.

2.3. Hydride transfer in heterodinuclear

organometallic complexes

Selective hydride transfer in dppe HPt–

. Ž

MCp CO MsMo, W was induced quantita-

tively on interaction with dimethyl acetylene-

dicarboxylate MeO₂CC[CCO₂Me to give

MHCp CO

and Pt MeO ₂CC[CCO ₂-

.Ž

Me dppe . However, in the reaction of 1 with

diphenylacetylene, only 58% conversion was

observed at room temperature, suggesting that

the reaciton is reversible. Accordingly, the inde-

Fig. 2. Eyring plot of the first order rate constants for the

Ž .

thermolysis of dppe EtPt–MoCp CO 3 .

.Ž

pendent reaction of Pt PhC[CPh dppe with

MoHCp CO afforded dppe HPt–MoCp CO

₃x

Na MoCp CO

11 equiv on the rate was

in ca. 40% conversion. A similar reaction of

W analogue 2 gave higher yields of the

observed k_obsds4.2=10^ys^y1under the

same conditions. Another possible pathway in-

cludes prior phosphine-dissociation giving a 3-

coordinate intermediate. However, exclusive

Ž . Ž

acetylene platinum 0 95% and hydridotung-

Ž .

sten II complexes 61% . Thus, the acetylene

induced b-hydrogen elimination reaction is con-

sidered to be a reversible process. Acetylene

having electron donating substituents such as

1-methyl-2-phenylacetylene and 1-pentyne did

not react at all with these heterodinuclear com-

plexes. Although detail mechanistic investiga-

tions were not carried out for this reversible

reaction, the reactions probably proceed by an

associative mechanism, since analogous associa-

tive route is known for alkyl transfer reactions

formation of the cationic complexes PtEt-

dppe PR₃

presence of excess amount of tertiary phosphine

ligands such as PMe₃and PPh₃prevents to

study such possibility experimentally see Ex-

perimental .

.Ž

x^qw

MoCp CO

₃x^y

Ž ..

Eq. 4 in the

dppe EtPtyMoCp CO qPR

dppe PtEt PR

MoCp CO

in dppe MePt–MCp CO which are also en-

RsMe,Ph

Ž .

hanced by electron deficient olefins. Coordina-

It is well established that b-hydrogen elimi-

tion of electron deficient acetylene is considered

nation from PtR₂L₂proceeds by a dissociative

mechanism giving a coordinatively unsaturated

reactive species from which a facile b-elimina-

tion takes place 25 . However, direct b-hydro-

gen elimination process from 4-coordinated

Ž .

Pt II complex is also known to proceed, if the

dissociation process of the tertiary phosphine

ligand is blocked 23 . In the present case,

strong coordiantion of the bidentate ligands is

Scheme 1.

(

)

S. Komiya et al.rJournal of Molecular Catalysis A: Chemical 159 2000 63–70

.Ž .

CPh dppe was prepared by the literature

not only to enhance the hydride transfer reac-

tion, but also to stabilize the zero-valent

method using PhC[CPh 30 . Solvents such as

THF, benzene, toluene, Et₂O and hexane were

distilled over benzophenone ketyl and stored

under nitrogen or argon. Reagents were pur-

Ž .

acetylene platinum 0 product.

chased and used as received. H, C H and

P H -NMR spectra were measured on a JEOL

LA-300 NMR 300.4 MHz for H apparatus

and the chemical shifts were given in ppm

relative to TMS for H and ¹³C, and to external

85% H₃PO₄for ³¹P. Infrared spectra were mea-

sured using KBr disk on JASCO FTrIR-410

spectrometer. Elemental analyses were per-

formed on a Perkin Elmer 2400 series II CHN

analyzer. GLC analyses were performed on a

Shimadzu GC-8 or a Shimadzu GC-14 B gas

liquid chromatography. Molar electric conduc-

tivities were measured on a TOA model CM-7

B instrument. Melting points were estimated

under nitrogen with a Yazawa capillary melting

apparatus and are uncorrected.

Ž .

3. Concluding remarks

Selective b-hydrogen elimination from eth-

ylplatinum complexes having transition metal as

a ligand gave new heterodinuclear hydridoplat-

inum–metal complexes by a non-dissociative

mechanism 20–23 . The hydrido ligand in the

heterodinuclear complexes moves from Pt to

(

)

(

)

4.2. Synthesis of dppe EtPt–MCp CO ₃

Mo or W on interaction with acetylene. These

reactions are similar to the alkyl transfer reac-

tion of alkylplatinum-transition metal heterodin-

Ž .

Preparation of dppe EtPt–MoCp CO

was shown as a typical experiment: the mixture

of PtEtCl dppe 150.0 mg, 0.2279 mmol and

silver nitrate 38.7 mg, 0.2279 mmol was stirred

at room temperature for 30 min in THF 15 ml

in the dark to give brown solid of silver chlo-

ride. The silver chloride was removed by filtra-

tion and the solution was added NaMoCp CO

240.8 mg, 0.9025 mmol at y208C. The reac-

tion mixture was stirred for 2 h at y208C. The

orange solution was evaporated to dryness un-

der reduced pressure to remove all volatile mat-

ters. The resulting orange solid was extracted

with toluene and the extract was concentrated.

Addition of hexane to the toluene solution and

then cooling at y308C gave orange crystals of

3 112.4 mg, 0.1286 mmol, 57% . Complexes 4

and 5 were prepared analogously. The yields,

analytical data, spectroscopic and physical data

for these complexes are summarized in Tables 1

and 2.

uclear complexes 13–18 and regarded as pref-

erential reductive elimination of the hydride and

transition metal at Pt. Such reactions may re-

flect the high mobility of hydride or organic

moieties on the heterogeneous metal catalyst

surface, where such hydride or organic group

would meet a possible site suitable for a next

catalytic reaction.

. Ž

4. Experimental

4.1. General

All manipulations were carried out using

standard Schlenk and vacuum techniques.

w x

PtEtCl dppe

26,27 , NaMoCp CO

28 ,

³x

NaWCp CO

prepared by literature methods. Pt PhC[

28 and NaCo CO

29 were

(

)

S. Komiya et al.rJournal of Molecular Catalysis A: Chemical 159 2000 63–70

(

)

(

)

4.3. Synthesis of dppe HPT–MCp CO ₃

gas 1.10 ml was introduced into the Schlenk

tube by using a hypodermic syringe as an inter-

nal standard for GLC analysis. The reaction

mixture was placed in a thermostatted oil bath

. Ž .

Preparation of dppe HPt–MoCp CO 1 is

shown as a typical example: 3 0.1254 g, 0.1445

mmol was dissolved in toluene and was heated

80"18C . A small gas sample 20 ml was

periodically obtained by a gas-tight syringe and

the generated gases were quantitatively ana-

lyzed by GLC. On the other hand, the time-

at 808C for 6 h, during which the color of the

solution turned from orange to deep green yel-

low. The solution was filtrated and all volatile

matters were removed under reduced pressure.

Crystallization of the resulted oily material from

a benzenerhexane mixture gave yellow plates

course of the formation of hydride complexes

was also followed by H NMR. 3 8.7 mg,

0.010 mmol was placed into a NMR tube and

toluene-d₈600 ml was introduced into the

. Ž

of 1 0.0594 g, 0.708 mmol, 49% . dppe EtPt–

NMR tube by a trap-to-trap method. 1,4-Di-

Ž .

4 was prepared by the similar

WCp CO

oxane 0.0064 mmol was added by a hypoder-

mic microsyringe as an internal standard. Then

the reaction mixture was heated at 808C as

method. The yields and physical and spectro-

scopic data of 1 and 2 involving elemental

analyses were shown in Tables 1 and 2.

above and the H NMR spectrum was periodi-

cally measured.

(

)

(

) ( )

4.4. Synthesis of dppe EtPt–Co CO ₄

The estimated rate constants by GLC are as

follows: k_obs=10⁴

s4.0 1 3 , 2.8 1

Ž . Ž .

Ž .

. Ž

Mixing of PtEtCl dppe 354.8 mg, 0.539

mmol with silver nitrate 91.5 mg, 0.539 mmol

in THF 15 ml at room temperature for 30 min

gave brown precipitate of silver chloride. The

precipitate was filtered off and the resulting

solution was added into NaCo CO 220.8 mg,

1.13 mmol . The solution was stirred at y208C

Ž .

Ž . Ž .

Ž . Ž

4 , 12 2 5 and 0.78 3 PtEtCl dppe . The

estimated rate constants by NMR are as follows:

_obs=10⁴

s3.7 3 and 2.7 4 .

Ž .

. Ž

[

(

)(

)]^q

4.6. Synthesis of PtEt dppe PPh₃

) ]^y

MoCp CO ₃

[

(

for 2 h. The yellow solution was evaporated to

dryness under reduced pressure to remove all

volatile matters. The resulting orange solid was

extracted with toluene and the extract was con-

centrated. Addition of hexane into the toluene

solution and then cooling at y308C gave or-

.Ž

x^qw ₃x^y

MoCp CO was pre-

PtEt dppe PPh₃

pared as follows: 3 79.6 mg, 0.123 mmol was

dissolved into benzene 2 ml and then triph-

enylphosphine 26.5 mg, 0.101 mmol was

added into the solution. The reaction mixture

was stirred for 2 days at room temperature. The

removal of all volatile matters from the light

yellow solution gave brown oil. Crystallization

of the oil from CH₂Cl₂rEt₂O gave yellow crys-

ange crystals of 5 246.8 mg, 0.329 mmol,

61% .

4.5. Kinetic measurement of b-hydrogen elimi-

(

)

nation of 3–5 and PtEtCl dppe

x^qw ₃x^yŽ

MoCp CO

tals of dppe EtPt PPh₃

79.8

mg, 77% yield . Molar electric conductivity L

As a typical example, kinetic measurement of

s1.99 S cm^ymol^y1. m.p. 1128C. H NMR

. Ž

300 MHz, CDCl₃: d 0.12 dt, 3H, J_{H – P}s14.4

3 was described. Diphenylmethane 2.00 ml

was added into a Schlenk tube containing 3

Hz, J_{H – H}s7.2 Hz, PtCH₂C H₃, 1.0–1.4 br,

. Ž

10.0 mg, 0.0113 mmol by using a pipet. The

2H, PtC H₂CH₃, 2.2–2.5 m, 4H, PC H₂C H₂P ,

Schlenk tube was capped with a rubber septum

and degassed for three times by freeze–pump–

thaw cycles. Then, a settled amount of methane

5.19 s, 5H, Cp , 7.2–7.5 br, 35H, Ph . P H

NMR 121.6 MHz, CDCl₃: d 25.8 dd, 1P,

J_{P – P}s373.2, 19.4 Hz, J_{Pt – P}s2948.8 Hz,

(

)

S. Komiya et al.rJournal of Molecular Catalysis A: Chemical 159 2000 63–70

PPh₃, 46.5 dd, 1P, J_{P – P}s19.4, 4.9 Hz, J_{P – Pt}

duced into the NMR tube by vacuum distilla-

tion. The NMR tube was rotated at room tem-

perature for 2 days to give 1 in 40% yield with

40% conversion.

s1565.6 Hz, dppe , 52.1 dd, 1P, J_{P – P}s373.2,

4.9 Hz, J_{P – Pt}s2941.5 Hz, dppe . IR KBr,

cm^y: 1893, 1774, 1767.

.Ž

x^qw

₃x^y

PtEt dppe PMe₃

prepared similarly and characterized spectro-

scopically. H NMR 300 MHz, CDCl₃: d

MoCp CO

was

References

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w x

Ž .

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J_{H – Pt}s22.5 Hz, PMe₃, 1.25–1.37 overlapped

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with the peak at d 1.31, 2H, PtC H₂CH₃, 2.34–

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2.45 m, 4 H, PC H₂C H₂P , 5.14 s, 5 H, Cp ,

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7.5–7.6 br, 35 H, Ph . P H NMR 121.6

w x

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w x

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C. Bianchini, A. Meli, J. Chem. Soc., Dalton Trans. 1996

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801.

w x

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1P, J_{P – P}s18.2, 3.6 Hz, J_{P – Pt}s1535.2 Hz,

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(

)

(

)

4.7. Reaction of dppe HPt–MCp CO ₃with

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10 F. Ozawa, T. Hikida, K. Hasebe, T. Mori, Organometallics

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mmol as an internal standard were added, and

14 A. Fukuoka, T. Sadashima, T. Sugiura, X. Wu, Y. Mizuho,

then benzene-d₆600 ml was introduced by

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dimethyl acetylenedicarboxylate 1.7 ml, 0.014

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mmol was added by a microsyringe. The NMR

17 A. Fukuoka, S. Fukagawa, M. Hirano, S. Komiya, Chem.

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tube was rotated mechanically for 2 days at

room temperature. The NMR spectrum of the

reaction mixture showed the formation of

Pt MeO₂CC[CCO₂Me dppe

MoHCp CO 100% 31 . The treatment of 1

18 T. Yasuda, A. Fukuoka, M. Hirano, S. Komiya, Chem. Lett.

1998 29.

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.Ž

. w x

20 H.E. Bryndza, J. Chem. Soc., Chem. Commun. 1985 1696.

100% and

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(

)(

)

4.8. Reaction of Pt PhC[CPh dppe with Mo-

2079.

(

)

HCp CO ₃

25 T.J. McCarthy, R.G. Nozzo, G. Whitesides, J. Am. Chem.

Soc. 103 1983 1676.

.Ž

Pt PhC[CPh dppe

mmol , MoHCp CO

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internal standard were added into a 5 mmf

16.6 mg, 0.0215

6.3 mg, 0.023 mmol

26 H.E. Bryndza, J.C. Calabrese, M. Marsi, D.C. Roe, W. Tam,

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NMR tube. Benzene-d₆600 ml was intro-

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Article Doi

Synthesis of hydridoplatinum-molybdenum (or tungsten) heterodinuclear complexes by β-hydrogen elimination of (dppe)EtPt-MCp(CO)3. Selective hydride transfer from Pt to Mo (or W)

DOI: 10.1016/S1381-1169(00)00171-0

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Full text of DOI:10.1016/S1381-1169(00)00171-0

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