Synthesis of ruthenium vinylidene complexes with dppe ligand and their cyclopropenation reaction

DOI: 10.1016/S0022-328X(97)00629-3

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Journal of Organometallic Chemistry p. 417 - 425 (1998)

Update date:2022-08-05

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Authors:

Chang, Chao-Wan

Ting, Pei-Chen

Lin, Ying-Chih

Lee, Gene-Hsiang

Wang, Yu

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Article abstract of DOI:10.1016/S0022-328X(97)00629-3

A number of cationic ruthenium vinylidene complexes [Ru]=C=C(Ph)CH₂R⁺ ([Ru]=(η⁵-C₅H₅)(dppe)Ru, dppe=Ph₂PCH₂CH₂PPh₂, 5a, R=CN; 5b, R=C₆F₅; 5c, R=Ph; 5d, R=p-C₆H₄CN; 5e, R=p-C₆H₄CF₃; 5f, R=1-C₁₀H₇; 5g, R=CO₂CH₃) are prepared from electrophilic addition of organic halides to the acetylide complex [Ru]-CCPh at the boiling point of CHCl₃. Complex 5g′, prepared at room temperature, displays similar spectroscopic property as that of 5g but is easily hydrolyzed to give [Ru]COCH₂Ph (6). Cyclopropenation of the organic vinylidene moiety of 5a-5f is accomplished in acetone by deprotonation of 5 with n-Bu₄NOH yielding the neutral cyclopropenyl complexes (7a, R=CN; 7b, R=C₆F₅; 7c, R=Ph; 7d, R=p-C₆H₄CN; 7e, R=p-C₆H₄CF₃; 7f, R=1-₁₀H₇). Protonation of 7b-7f regenerates the corresponding vinylidene complexes. In the presence of allyl iodide, opening of the three-membered ring of 7a, followed by a subsequent oxidative coupling reaction, gives a dimeric dicationic product {[Ru]=C=C(Ph)-CHCN}₂⁺² (9a). In the processes of preparing the starting material Cp(dppe)RuCl for the acethylide complex, two dppe complexes Ru(dppe)₂Cl₂ (2) and [Cp(dppe)RuCl]₂ (3) are isolated. Molecular structures of complexes 2, 3, 6, and 7b have been confirmed by X-ray diffraction analysis.

Full text of DOI:10.1016/S0022-328X(97)00629-3

Journal of Organometallic Chemistry 553 1998 417–425

Synthesis of ruthenium vinylidene complexes with dppe ligand and their

cyclopropenation reaction

)

Chao-Wan Chang, Pei-Chen Ting, Ying-Chih Lin , Gene-Hsiang Lee, Yu Wang

Department of Chemistry, National Taiwan UniÕersity, Taipei 106, Taiwan

Received 29 July 1997; received in revised form 15 September 1997

Abstract

w x Ž .

number of cationic ruthenium vinylidene complexes Ru 5C5C Ph CH₂R

Žw

.Ž

Ru 5 h -C₅H₅dppe Ru, dppe s

Ph₂PCH₂CH₂PPh₂, 5a, RsCN; 5b, RsC₆F₅; 5c, RsPh; 5d, Rsp-C₆H₄CN; 5e, Rsp-C₆H₄CF₃; 5f, Rs1-C₁₀H₇; 5g,

RsCO₂CH₃are prepared from electrophilic addition of organic halides to the acetylide complex Ru –C[CPh at the boiling point of

CHCl₃. Complex 5g^X, prepared at room temperature, displays similar spectroscopic property as that of 5g but is easily hydrolyzed to give

Ž .

Ru COCH₂Ph 6 . Cyclopropenation of the organic vinylidene moiety of 5a–5f is accomplished in acetone by deprotonation of 5 with

n-Bu₄NOH yielding the neutral cyclopropenyl complexes

7a, RsCN; 7b, RsC₆F₅; 7c, RsPh; 7d, Rsp-

C₆H₄CN; 7e, Rsp-C₆H₄CF₃; 7f, Rs1-₁₀H₇. Protonation of 7b–7f regenerates the corresponding vinylidene complexes. In the

presence of allyl iodide, opening of the three-membered ring of 7a, followed by a subsequent oxidative coupling reaction, gives a dimeric

dicationic product Ru 5C5C Ph –CHCN

complex, two dppe complexes Ru dppe Cl₂2 and Cp dppe RuCl 3 are isolated. Molecular structures of complexes 2, 3, 6, and 7b

Äw

4^q

9a . In the processes of preparing the starting material Cp dppe RuCl for the acethylide

x Ž .

²Ž .

have been confirmed by X-ray diffraction analysis. q 1998 Elsevier Science S.A.

Keywords: Organic halides; Allyl iodide; Oxidative coupling reaction

1. Introduction

system. In addition, the process of preparing the starting

material, two by-products were isolated and the struc-

ture determination is also described.

During the course of investigations into ruthenium

vinylidene chemistry, we previously reported the forma-

tion of several interesting neutral cycloropenyl com-

2. Results and discussion

w x

1 . F o r ex am p le, C p P P h ₃-

p lex es

Ru5C5C Ph CH₂CN in acetone was found to un-

2.1. Preparation of metal dppe complex

dergo deprotonation to afford the yellow crystalline

cyclopropenyl complex

Treatment of Cp PPh_{3 2}RuCl with dppe in benzene

Ž .

The cationic charge along with the electron-withdraw-

ing CN group appending to the vinylidene ligand make

the protons at the g-carbon acidic enough for facile

deprotonation. This reaction generates a racemic mix-

ture of the products with an asymmetric carbon at the

three-membered ring. To elaborate the breadth of such a

system, we set to study the ruthenium complex with the

bidentate dppe ligand. Herein, we report results on this

affords the light yellow product Cp dppe RuCl 1 in

ca. 70% yield 2,3 . Complex 1 is soluble in benzene. In

addition to 1, some by-products are isolated as orange–

yellow precipitates from which two ruthenium chloride

Ž . w x x

complexes Ru dppe Cl₂2 4 and Cp m-dppe RuCl

Ž .

were separated by recrystallization from

CH₂Cl₂rhexane as yellow and red crystals, respec-

tively Table 1. The yield of 2 is about 20% and the

yield of 3 is approximately 5%. In the ³¹P NMR

spectrum of 2 in CDCl₃at room temperature, the singlet

resonance at d 45.75 is assigned to the dppe ligand

indicating high symmetry of the complex. Similarly in

)

Corresponding author.

0022-328X

(

)

418

C.-W. Chang et al.rJournal of Organometallic Chemistry 553 1997 417–425

Ž .

Fig. 2. An ORTEP drawing of Cp₂dppe ₂Ru₂Cl₂3 with thermal

Ž .

2 with thermal

Fig. 1. An ORTEP drawing of dppe ₂RuCl₂

ellipsoids shown at the 50% probability level.

the ³¹P NMR spectrum of 3, the singlet resonance at d

37.05 is observed. Formation of complex 2 has been

reported from the reaction of RuCl₃PxH₂O with dppe

however the structure has not been determined. There-

fore, we carried out structure determination of 2 and 3

by single-crystal X-ray diffraction analysis and ORTEP

drawings of 2 and 3 are shown in Fig. 1 and Fig. 2,

respectively. Both complexes contain center of symme-

try. In 2, which contains no Cp ligand, the two bidentate

dppe ligands and the two chloro ligands form a pseudo

octahedral geometry around the ruthenium metal center

slightly longer than the corresponding ones 2.311 2 ,

Ž .

2.326 2 A in dinuclear complex 3 containing a Cp

ligand in each metal center. And the Ru–Cl distance

2.433 1 A of 2 Table 2 is slightly shorter than the

Ž .

corresponding one 2.506 2 A in 3 Table 3. The two

dppe ligands in 3 bridge two metal centers with the

Ž . Ž . Ž .

Ž .

P 1 –C 1 –C 2 and P 2 –C 2 –C 1 angles 115.9 5

Ž . .

and 110.2 5 8 approximately the same as that 112.3 3

Ž . .

and 114.2 3 8 of the bidentate one in 2. The acetylide

Ž .

complex Ru -C[CPh 4 is prepared by the reaction of

1 with PhC[CH in high yield and display identical

w x

spectroscopic properties as that in the literature 5 .

A are

Ž .

and the Ru–P distances 2.356 1 , 2.381 1

Table 1

Crystal and intensity collection data for dppe ₂RuCl₂2, Cp₂dppe ₂Ru₂Cl₂, 3, Cp dppe Ru COCH ₂C₆H ₅

, 7b

and

Molecular formula

Molecular weight

C₆₀H₆₄O₂P₄Cl₂Ru, 2

1113.02

C₃₂H₃₀P₂Cl₄Ru, 3

719.41

C₄₅H₄₈O₃P₃F₆Ru, 6

944.84

C₄₆H₃₅P₂F₅Ru, 7b

845.78

Space group

P 2₁rc

11.371 3

P 2₁rn

13.190 2

P 2₁rc

11.777 3

Ž .

a A

Ž .

12.094 7

Ž .

b A

Ž .

12.517 3

13.458 2

Ž .

17.166 5

Ž .

24.824 4

Ž .

15.433 5

Ž .

c A

Ž .

13.050 3

17.232 3

14.507 5

Ž .

a 8

Ž .

94.19 2

Ž .

b 8

Ž .

96.02 2

Ž .

102.08 2

Ž .

105.87 3

Ž .

91.33 3

Ž .

94.72 3

Ž .

2622.5 9

V A

3211.9 15

4339.9 19

1962.8 13

Crystal dimension mm

0.20=0.30=0.50

0.32=0.40=0.50

0.10=0.50=0.50

0.10=0.15=0.30

28–458

Radiation

2u range

Scan type

Total number of reflections

unique reflections I)2s I

Mo K a ls0.7093 A

28–508

ur2u

4597

2839

0.039

0.038

5650

4145

0.054

0.064

7586

5196

0.049

0.056

5109

2498

0.053

0.050

Ž .

R_w

(

)

C.-W. Chang et al.rJournal of Organometallic Chemistry 553 1997 417–425

419

Table 2

Ž .

8 of

Selected interatomic distances

and bond angles

dppe ₂RuCl₂, 2

Ru–Cl

Ž .

Ž . Ž .

P 1 –C 9

Ž .

1.836 5

2.4325 12

Ž . Ž .

P 2 –C 2

Ž .

1.850 5

Ru–C 1

Ru–P 2

2.3563 13

Ž .

Ž . Ž .

Ž .

1.845 5

2.3811 13

P 2 –C 15

Ž .

1.841 5

P 1 –C 1

Ž . Ž .

1.843 5

P 2 –C 21

Ž .

Ž . Ž .

Ž .

1.529 7

P 1 –C 3

1.823 5

C 1 –C 2

Ž .

85.81 4

Ž .

81.62 5

Cl–Ru–P 1

Cl–Ru–P 1 a

Cl–Ru–P 2

Cl–Ru–P 2 a

P 1 –Ru–P 2

Ž .

Ž . Ž .

P 1 –Ru–P 2 a

Ž .

98.38 5

94.19 4

81.40 4

98.60 4

Ž .

Ž . Ž . Ž .

Ž .

112.3 3

P 1 –C 1 –C 2

Ž . Ž . Ž .

P 2 –C 2 –C 1

Ž .

114.2 3

2.2. Preparation of Õinylidene complexes

Treatment of 4 with ICH₂CN at refluxing tempera-

ture of CHCl₃affords the cationic vinylidene complex

q y

Ru 5C5C Ph CH₂CN I 5a in 83% yield. In the

presence of excess NH₄PF₆, the counter anion is re-

placed by PF₆^y. Unlike other vinylidene complexes

which are normally prepared by treatment of an acetylide

complex with primary organic halide at room tempera-

ture for 1 d, complex 5a is prepared by heating the

chloroform solution of 4 and primary alkyl halide to

reflux for ca. 10 h. The reaction at room temperature

also gives the product with the same spectroscopic data

but such a product is relatively less stable. Similarly,

. Ž .

Fig. 3. An ORTEP drawing of Cp dppe Ru COCH₂C₆H₅6 with

thermal ellipsoids shown at the 50% probability level.

dene complexes, prepared by carrying out the reaction

at room temperature, is easily cleaved in the presence of

acid. In addition, the hexafluorophosphate salt NH₄PF₆

used for the preparation is easily converted to HPF₆.

Thus complex 5g^Xwith PF₆^ycounter anion prepared at

room temperature is unstable when dissolved in

preparation of other vinylidene complexes

CH₂Cl₂rhexane solution. It decomposes to give the

Ru 5C5C Ph CH₂R 5b, RsC₆F₅; 5c, RsPh; 5d,

acyl complex Ru C O CH₂Ph 6 . With Br anion, 5g^X

is stable for a period of 2 d and then decomposes to

some unidentified products. Complexes 5a^Xand 5b^X

both with PF₆^yanion are prepared at room temperature,

they also decompose to give 6 but with the halide as the

counter anion they are relatively more stable. It seems

that the presence of HPF₆is required for the formation

of 6.

Ž .

Rsp-C₆H₄CN; 5e, Rsp-C₆H₄CF₃; 5f, Rs1-C₁₀H₇;

5g, RsCOOCH₃have been accomplished by reacting

4 with the corresponding halides at refluxing tempera-

ture of CHCl₃all with high yields. Interestingly, 5a is

soluble in acetone and insoluble in CH₃CN, CHCl₃and

CH₂Cl₂. Complexes 5b–5g are all soluble in polar

solvent such as CHCl₃, CH₂Cl₂, MeOH and CH₃CN

but insoluble in acetone, ether and hexane. All 5a–5g

prepared at higher temperature are quite stable even in

solution. They display pink to orange color in their solid

state. The characteristic spectroscopic data of these

vinylidene complexes consist of strongly deshielded C_a

resonance as a triplet at d 340"5 in the ¹³C NMR

spectrum and a singlet ³¹P NMR resonance normally at

around d 77"1 in CDCl₃at room temperature, which

is due to the fluxional behavior of the vinylidene ligand

In the ³¹P NMR spectrum of 6, a singlet resonance at

d 91.10 is observed. The structure of 6 is determined by

a single crystal X-ray diffraction analysis. An ORTEP

drawing is shown in Fig. 3. The acyl ligand is clearly

seen with the acyl plane Ru, C1, C2, O1 bisecting the

P1–Ru–P2 angle Table 4. Such a transformation has

w x

been observed in other vinylidene complexes 8 . Pre-

6,7 .

The newly formed carbon–carbon bond of the vinyli-

Table 4

Ž .

8 of

Selected interatomic distances

and bond angles

Cp dppe Ru COCH₂C₆H₅, 6

Ž .

Ru–P 2

Ž . Ž . Ž .

2.2655 17 O 1 –C 1

2.2713 17 C 2 –C 3

Ž .

1.328 7

1.509 10

Ru–P 1

Ž .

Table 3

Ž . Ž .

Ž .

Selected interatomic distances

and bond angles

Ž .

1.530 10

Ž .

Ru–C 1

1.992 6

C 9 –C 10

1.496 10

Cp₂dppe ₂Ru₂Cl₂, 3

Ž . Ž .

C 1 –C 2

Ž .

88.45 17

93.83 17

Ž . Ž . Ž .

Ž .

Ru–P 1

2.3105 20 Ru–Cl 1

2.5060 20

P 1 –Ru–P 2

P 1 –Ru–C 1

P 2 –Ru–C 1

84.99 6

O 1 –C 1 –C 2

110.6 5

Ž .

Ž . Ž .

Ž .

Ž . Ž . Ž .

Ž .

Ru–P 2

Ž .

2.3263 20 C 1 –C 2 a

1.513 10

C 1 –C 2 –C 3

117.3 5

Ž .

Ž . Ž . Ž .

Ž .

Ž . Ž .

Ž .

P 1 –Ru–P 2

P 1 –Ru–Cl 1 93.93 7

Ž . Ž . Ž .

P 2 –Ru–Cl 1 93.95 6

96.99 7

P 1 –C 1 –C 2 a 115.9 5

P 1 –C 9 –C 10 111.7 5

Ž . Ž . Ž .

Ž . Ž .

Ž .

Ž . Ž . Ž .

Ž .

P 2 –C 2 –C 1 a 110.2 5

Ru–C 1 –O 1 127.9 5

P 2 –C 10 –C 9 111.8 5

Ž . Ž .

Ru–C 1 –C 2

121.5 4

(

)

420

C.-W. Chang et al.rJournal of Organometallic Chemistry 553 1997 417–425

sumably, protonation at C_bof the acetylide complex

followed by hydroxy-attack at the C_aled to the prod-

uct. If complex 5 is prepared by thermolysis in CHCl₃

solution, no such transformation is observed. For exam-

ple, treatment of 5g, prepared at refluxing temperature

of CHCl₃, with CH₃COOH, H₂O or NH₄PF₆for 3

days results in recovery of the starting material. The

vinylidene complexes 5 and 5^Xprepared at room tem-

perature and at 558C display similar spectroscopic fea-

tures but their reactivities are quite different.

was recovered. Better donor ability of the dppe along

with the ester group appending to the vinylidene ligand

may make the methylene protons less acidic in 5g thus,

deter the deprotonation process.

Synthesis of metal cyclopropenyl derivatives in which

the metal bonds to C sp of the cyclopropene ring in

this case the three-membered ring can be viewed as an

antiaromatic cyclopropenide ions have been reported in

the literature 9–13 . However, to our knowledge, only

few example of such derivative in which the metal is

bonded to the C sp of the three-membered ring has

been reported 14 . A few structurally different transi-

tion metal cyclopropenylidene complexes, mostly pre-

2.3. Deprotonationr cyclopropenation of Õinylidene

complexes

pared from dichlorocyclopropene 15–17 and a number

Deprotonation of 5a by n-Bu₄NOH in acetone in-

duces a cyclization reaction and yields the neutral cy-

of p-cyclopropene complexes 18–21 are also known.

The acidity of the aliphatic protons on a coordinated

dppe ligand in a cationic iron vinylidene complex 22

has been employed for inducing the intramolecular cy-

clization between the dppe and vinylidene ligand.

. Ž

clopropenyl complex

7a see

Scheme . No cyclopropenation reaction is observed in

CH₃CN. The light orange–yellow crystalline product

forms directly in the reaction mixture and can be ob-

tained in analytically pure form by filtration. Complex

7a is stable and is soluble in CH₂Cl₂, CHCl₃, and THF

but insoluble in ether, n-hexane, MeOH and CH₃CN. In

the ¹H NMR spectrum of 7a, the resonance of the

methyne proton of the three-membered ring appears at

2.4. Molecular structure of the Ru cyclopropenyl com-

plex 7b

The molecular structure of 7b has been determined

by X-ray diffraction study. An ORTEP drawing of 7b is

shown in Fig. 4. The cyclopropenyl ring is clearly seen

d 2.13. The ³¹P NMR spectrum of 7a displays two

doublet resonances at d 90.14 and 88.47 with J_{P – P}

with the pentafluorophenyl group bound to the unique

Ž .

24.3 Hz assignable to the two non-equivalent phospho-

rus atoms of the dppe ligand arising from the asymmet-

ric cyclopropenyl ring.

sp carbon. The Ru–C 1 bond length of 2.009 10 A

Table 5 is typical for a Ru–C sp single bond and the

Ž . Ž .

C 1 –C 3 bond length of 1.310 14 A is a double

bond, indicating coordination of the sp²carbon of the

The deprotonationrcyclopropenation process in ace-

tone is a general reaction for a number of vinylidene

complexes. Namely, the same reaction occurs for simi-

lar complexes 5b–5f giving cyclopropenyl complexes

Ž . Ž .

cyclopropenyl ligand. The bond angles Ru–C 1 –C 3

and C 1 –C 3 –C 4 of 165.6 4 8 and 154.0 5 8, respec-

tively, are both far greater than that of an idealized

Ž . Ž . Ž .

Ž .

, 7b, RsC₆F₅; 7c, RsPh; 7d,

R s p-C₆H₄CN; 7e, R s p-C₆H₄CF₃; 7f, R s 1-

C₁₀H₇, respectively. Spectroscopic data of complexes

7 are similar. The single crystals of 7b suitable for

X-ray diffraction analysis are obtained when the reac-

tion is carried out at lower concentration. Complexes

7c–7f are not stable in solution. Presence of the

pentafluorophenyl group in 7b exceptionally stabilizes

the complex. Thus, complex 7b is stable in CHCl₃, but

other cyclopropenyl complexes decompose in CHCl₃

within 10 h. Facile deprotonation of 5 by n-Bu₄NOH

indicates acidic nature of the methylene protons of

5a–5f, which may be associated with the combined

influence of the cationic character, the electron with-

drawing substituent and the benzylic property of the

vinylidene complexes. It also appears that the hybridiza-

tion of the C_datom should be sp²for the cyclopropena-

tion reaction to occur. Complex 5g failed to yield the

deprotonation product in the presence of Bu₄NOH. We

previously observed formation of cyclopropenyl and

furanyl products for the bistriphenylphosphine analogue

of 5g. But with the dppe ligand, the starting material

Fig. 4. An ORTEP drawing of Cp dppe Ru–C5C C₆H₅CH C₆F₅

. Ž

ligand eliminated for clarity.

7b 50% thermal ellipsoids with the phenyl groups on the dppe

(

)

C.-W. Chang et al.rJournal of Organometallic Chemistry 553 1997 417–425

421

Table 5

2.6. OxidatiÕe coupling reactions of metal cyclo-

propenyl complex

Ž .

8 of

Selected interatomic distances

and bond angles

Cp dppe Ru C5C Ph CH C₆F₅, 7b

Ž . Ž . Ž . Ž .

Ru–P 2 2.231 3 C 2 –C 3

Ru–P 1 2.237 3 C 1 –C 3

1.310 14

1.467 15

Treatment of 7a with 20 fold excess of allyl iodide

Ž . Ž . Ž . Ž .

affords the dimeric dicationic vinylidene complex

Ž .

1.453 16

1.463 14

Ru–C 1 2.009 10 C 2 –C 10

4^q2

Ru 5C5C Ph CHCN

9a . Other organic iodides

Ž . Ž .

C 1 –C 2 1.584 16 C 3 –C 4

C 16 –C 17

Ž .

1.529 15

such as methyl iodide, ethyl iodide and iodobenzene

does not generate the coupling product. No similar

product was obtained in the reactions of 7b or 7c with

allyl iodide. Complex 9a is insoluble in most of the

organic solvents and only sparingly soluble in DMSO

wherein it forms an orange colored solution. The mass

Ž . Ž .

P 1 –Ru–P 2

84.60 12

C 1 –C 2 –C 10

119.7 10

Ž .

122.8 9

Ž .

Ž . Ž .

Ž .

Ž . Ž .

P 1 –Ru–C 1

Ž . Ž .

81.0 3

90.8 3

C 3 –C 2 –C 10

Ž .

Ž . Ž . Ž .

P 2 –Ru–C 1

C 1 –C 3 –C 2

69.3 8

Ž . Ž .

Ž .

Ž . Ž . Ž .

Ru–C 1 –C 2

133.9 7

Ž .

C 1 –C 3 –C 4

154.0 10

Ž . Ž .

Ž . Ž . Ž .

Ru–C 1 –C 3

165.6 8

C 2 –C 3 –C 4

136.5 10

Ž .

P 1 –C 17 –C 16 107.5 6

Ž . Ž . Ž .

Ž .

60.0 7

Ž .

50.7 6

Ž .

C 2 –C 1 –C 3

P 2 –C 16 –C 17 110.5 7

Ž . Ž . Ž .

Ž . Ž .

C 1 –C 2 –C 3

spectrum of 9a is consistent with the formulation

Ru 5C5C Ph CHCN I . In the ³¹P NMR spectrum

of 9a, the chemical shift of the resonances at d 76.34

and 75.28 is comparable to that observed for 5a.

Apparently a cationic ruthenium vinylidene radical

24,25 may be formed at the initial stage of the reaction

Ž . Ž .

C sp hybridization. The C 1 –C 2 and C 2 –C 3

of 7a with C₃H₅I. Oxidative coupling of such a radical

satisfactorily accounts for the formation of the product

9a. Previous example of oxidative carbon–carbon cou-

pling of the cationic iron vinylidene complex

Ž .

bond lengths of 1.58 2 and 1.47 2 A, respectively, are

significantly different, conforming with the favorable

cleavage of the C 1 –C 2 bond described below. The

phenyl group on the three-membered ring is approxi-

mately coplanar with the cyclopropene and lies far away

from the Cp.

Ž . Ž .

x^q

Cp dppe Fe5C5CHMe leading to the formation of

a dimer Cp dppe Fe5C5CMe ₂has been reported

x^q2

w x

26 , whereas a very similar coupling 27 reaction has

been attributed to the presence of 17 electron species

confirmed by ESR 28 , The coupling of allyl radical

resulting in formation of bicyclopropyl molecule 29

2.5. Electrophilic additions of ruthenium cyclopropenyl

complexes 7

and radical annulations of allyl iodomalononitriles 30

have been reported in the literature. Unsubstituted

vinylidene complex Cp PPh_{3 2}Ru5C5CH₂also under-

Addition of CF₃COOH at y608C to 7a regenerates

5a in quantitative NMR yield indicating basic character

of the methyne carbon of the three-membered ring. But

if the reaction is carried out at room temperature, in

addition to 5a, an unidentified product is observed. This

ring opening process by protonation is different from

the acid induced demethoxylation of the iron cyclo-

goes oxidative coupling in the presence of MeI and

generates a similar dimer 31 . There are also few

examples of metal acetylide couplings 32–34 . Possible

role of azavinylidene 35 in the conversion of nitriles to

diimido-bridged dimer in tantalum and niobium com-

plexes 36–38 has been recently addressed. These ex-

amples are, nevertheless, different from what is ob-

served in 7a, namely in our system the oxidative cou-

pling at C_gresults in formation of a C₆bridge between

the two Ru metal centers. Unlike the phosphine ana-

propenyl complex 14 . Treatment of 7b with HgCl₂

a lso a ffo rd s th e v in y lid e n e p ro d u c t

4^q

Ru 5C5C Ph CH C₆F₅HgCl

8b . In the H NMR

w x

spectrum of 8b in CDCl₃, the resonance at d 3.38 is

assigned to the methyne proton near the HgCl group.

And in the ³¹P NMR spectrum the two resonances at d

78.59 and 78.10 with J_{P – P}s18.2 Hz assignable to the

dppe are due to the asymmetric center at the C_g. In the

FAB MS spectrum, the parent peak for the cation is

observed at mrzs1083.1. The vinylidene complexes

5a and 8b are formed by selective cleavage of the single

bond of the cyclopropenyl ring near the metal center.

This selectivity is similar to that reported for the unsym-

metrical organic cyclopropenes where the single bond

logue 1 , the dppe dimer 9a does not undergo deproto-

nation to yield the bis cyclopropenyl complex.

2.7. Conclusion

The preparation of neutral Ru cyclopropenyl com-

plexes containing dppe ligand has been accomplished

by deprotonation of a CH or CH₂unit at C_gof the

cationic vinylidene complexes in acetone. Preparation

of complexes with various substituents such as CN, Ph

and 1-naphthyl groups at CH or CH₂renders this

preparation a potentially versatile synthetic method.

Protonation of the cyclization products regenerates the

vinylidene complexes indicating the nucleophilic nature

of the antecedent C_gcarbon of the vinylidene ligand.

with a methyl substituent is cleaved 23 . Attempts to

carry out cyclopropenation of 8b by using n-Bu₄NOH,

n-Bu₄NF and DBU result in cleavage of the C–Hg

bond yielding 5b.

(

)

422

C.-W. Chang et al.rJournal of Organometallic Chemistry 553 1997 417–425

Thus, other electrophiles could also be added to this

same C_gsite by reaction with cyclopropenyl complex.

M –2Cl . Anal. Calcd. for C₆₂H₅₈Cl₂P₄Ru₂: C, 62.05;

H, 4.87; Anal. Found: C, 61.78; H, 4.96.

[

(

)

(

)

][ ]

3.3. Synthesis of Cp dppe Ru5C5C Ph CH₂CN I ,

5a and other Õinylidene complexes

3. Experiment

3.1. Materials

a 20 ml CHCl₃solution of complex

Cp dppe RuC[CPh 0.50 g, 0.75 mmol , an aliquot of

All manipulations were performed under nitrogen

using vacuum-line, dry box, and standard Schlenk tech-

niques. CH₃CN and CH₂Cl₂were distilled from CaH₂

and diethyl ether and THF from Narketyl. All other

solvents and reagents were of reagent grade and were

used without further purification. NMR spectra were

recorded on the Bruker AC-200 and AM-300WB FT–

ICH₂CN 54.4 ml, 0.75 mmol was added. The solution

was heated to reflux for 12 h. Pink precipitates formed

while the solution was allowed to cool to room tempera-

ture. The solvent was removed under vacuum and 20 ml

of ether was added then the mixture was filtered and the

solid portion was washed with 20 ml of hexane and 20

ml of diethyl ether and dried under vacuum to give the

xw x .

NMR spectrometers at room temperature unless stated

product Cp dppe Ru5C5C Ph CH₂CN I , 5a 0.52 g

in 83% yield. Spectroscopic data of 5a: ¹H NMR

otherwise and are reported in units of d with residual

protons in the solvent as an internal standard CDCl₃, d

7.24; CD₃CN, d 1.93; C₂D₆CO, d 2.04 . FAB mass

spectra were recorded on a JEOL SX-102A spectrome-

ter. Complexes 1a and Cp dppe RuC[CPh 39 were

prepared following the method reported in the literature.

Elemental analyses and X-ray diffraction studies were

carried out at the Regional Center of Analytical Instru-

ment located at the National Taiwan University.

CDCl₃: 7.60–6.60 m, 25H, Ph , 5.60 s, 5H, Cp ,

3.50–2.90 m, 4H, CH₂, 2.52 s, 2H, CH₂CN . ³¹P

NMR CDCl₃: 76.50. C NMR CDCl₃: 364.2 t,

w x

J_{C – P}s15.1 Hz, C_a, 134.4–126.8 m, Ph and C_b,

122.1 CN , 92.5 Cp , 28.1 d, CH₂, J_{C – P}s10.0 Hz ,

102

18.4 s, CH₂CN . MS mrz, Ru

706.1 M , 593.1

Cp dppe RuCO ,565.1 Cp dppe Ru . Anal. Calcd.

for C₄₁H₃₆NP₂RuI: C, 59.14; H, 4.36; N, 1.68; Anal.

Found: C, 60.07; H, 4.29, N, 1.50; Complexes 5b yield

3.2. Preparation of Ru dppe complexes

81% , 5c yield 79% , 5d yield 71% , 5e yield 74%

and 5f yield 80% were prepared using similar proce-

dure. But for 5b–5f, the anion was replaced with PF₆^y

by adding NH₄PF₆to the cold solution after refluxing.

A Schlenk flask was charged with Cp PPh_{3 2}RuCl,

1a 2.00 g, 2.76 mmol and dppe 1.21 g, 3.05 mmol

and the atmosphere was replaced with nitrogen, then

S p e c t r o s c o p i c

d a t a

o f

C₆H₆60 ml was added. The resulting solution was

heated to reflux for 8 h to give a yellow solution with

some precipitates. After filtration, 20 ml of hexane was

added to the filtrate to bring about more precipitation

which was also filtered. The solid parts were combined

Cp dppe Ru5C5C Ph CH₂C₆F₅PF₆5b : H NMR

CDCl₃: 7.80–6.50 m, Ph , 5.58 s, 5H, Cp , 3.60–

2.90 m, 4H, CH₂, 2.80 s, 2H, CH₂C₆F₅. ³¹P NMR

CDCl₃: 76.97. C NMR CDCl₃: 343.0 t, J_{C – P}

12.1 Hz, C , 135.8–126.2 m, Ph , 112.3 C_b, 91.9

Ž^a

. Ž .

to give two minor products trans-RuCl₂dppe 2 and

Cp , 27.4 d, CH₂, J_{C – P}s24.3 Hz , 17.1 CH₂C₆F₅.

Ž .

RuClCp m-dppe

3 which could be separated by

MS mrz : 847.1

, 593.1 Cp dppe RuCO ,

recrystallization from 1:1 hexane:CH₂Cl₂. Complex 2

displays yellow and 3 displays red color. The solvent of

the clear solution was reduced to about 10 and 80 ml of

hexane was added. The yellow precipitates thus formed

were filtered and washed with diethyl ether and hexane

565.1 Cp dppe Ru . Anal. Calcd. for C₄₆H₃₆F₁₁P₃Ru:

C, 55.71; H, 3.66; Anal. Found: C, 55.90; H, 3.86.

Spectroscopic data of Cp dppe Ru5C5C Ph –

CH₂C₆H₅PF₆5c : ¹H NMR CDCl₃: 7.50–6.60

m, Ph , 5.52 s, 5H, Cp , 3.50–2.90 m, 4H, CH₂,

2.85 s, 2H, CH₂C₆H₅. P NMR CDCl₃: 77.65. ¹³C

to give the major product Cp dppe RuCl 1.15 g, 1.93

mmol, 70% yield . Spectroscopic data of trans-

NMR CDCl₃: 349.0 t, J_{C – P}s16.4 Hz, C , 138.0–

^aŽ

Ž .

RuCl₂dppe

2 : H NMR CDCl₃: 7.23–6.90 m,

126.5 m, Ph , 125.1 C_b, 91.7 Cp , 28.7 d, CH₂,

40H, 8Ph , 2.80–2.65 m, 8H, CH₂. P NMR CDCl₃:

45.75. C NMR CDCl₃: 135.6–126.8 m, Ph , 30.2

J_{C – P}s25.0 Hz , 29.6 CH₂C₆H₅. MS mrz : 757.1

M -PF₆, 593.1

Cp dppe RuCO

565.1

d, CH ₂, J_{C – P}s 12.1 Hz . Anal. Calcd. for

Cp dppe Ru . Anal. Calcd. for C₄₆H₄₁F₆P₃Ru: C,

C₅₂H₄₈Cl₂P₄Ru: C, 64.46; H, 4.99; Anal. Found: C,

61.26; H, 4.58; Anal. Found: C, 60.97; H, 4.67. Spec-

troscopic data of Cp dppe Ru5C5C Ph CH₂p-

64.30; H, 4.59. Spectroscopic data of RuClCp m-

Ž .

dppe

3 : H NMR CDCl₃:7.50–6.90 m, Ph , 3.85

C₆H₄CN PF₆5d : H NMR CDCl₃: 7.80–6.40 m,

s, Cp , 3.00–2.60 m, 8H, CH₂. P NMR CDCl₃:

37.05. C NMR CDCl₃: 130.0–127.0 m, Ph , 80.4

Ph , 5.59 s, 5H, Cp , 3.50–3.10 m, 4H, CH₂, 2.93 s,

2H, CH₂p-C₆H₄CN . P NMR CDCl₃: 77.40. ¹³C

s, Cp , 24.2 d, CH₂J_{C – P}s20.6 Hz . MS mre,

NMR CDCl₃: 347.2 t, J_{C – P}s18.1 Hz, C_a, 132.5–

FAB, 20 ev, Ru¹⁰²968.1 M , 932.2 M –Cl , 897.2

126.8 m, Ph , 118.7 C_a, 109.9 C_b, 88.1 Cp , 28.2

(

)

C.-W. Chang et al.rJournal of Organometallic Chemistry 553 1997 417–425

423

d, CH₂, J_{C – P}s46.8 Hz , 29.4 CH₂p-C₆H₄CN .

stirred at room temperature for 24 h. Then the solvent

was removed under vacuum and the residue was washed

with 2=20 ml of hexane and 2=20 ml of ether to give

MS mrz : 782.1 M –PF₆, 593.1 Cp dppe RuCO ,

565.1

C p dppe R u .

A nal. C alcd. for

C₄₇H₄₀F₆NP₃Ru: C, 60.91; H, 4.35; N, 1.51; Anal.

Found: C, 60.65; H, 4.30; N, 1.43. Spectroscopic data

of Cp dppe Ru5C5C Ph CH ₂p-C₆H ₄CF₃PF₆

the product 6 0.16 g, 64% yield . Spectroscopic data of

Ž .

6 : H NMR CDCl₃: 7.80–6.00 m, Ph , 4.84 s, 5H,

Cp , 3.38 s, 2H, CH₂, 3.00–2.50 m, 4H, CH₂. ³¹P

NMR CDCl₃: 91.10. C NMR CDCl₃: 254.4 t,

xw x

5e : H NMR CDCl₃: 7.50–6.40 m, Ph , 5.54 s,

5H, Cp , 3.20–2.80 m, 4H, CH₂, 2.91 s, 2H, CH₂p-

J_{C – P}s13.4 Hz, CO , 139.7–127.8 m, Ph and C_b

C₆H₄CF₃. ³¹P NMR CDCl₃: 77.33. ¹³C NMR

87.5 Cp , 60.9 COCH₂, 27.5 t, CH₂CH₂, J_{C – P}

Ž ^b

CDCl₃: 343.1 t, J_{C – P}s12.1 Hz, C_a, 135.8–126.2

22.5 H z . M S

m r z : 684.1

m, Ph , 112.3 C , 91.9 Cp , 27.7 d, CH₂, J_{C – P}

593.1 Cp dppe RuCO , 565.1 Cp dppe Ru . Anal.

Calcd. for C₃₉H₃₆OP₂Ru: C, 68.51; H, 5.31; Anal.

Found: C, 68.38; H, 5.49.

14.1 Hz , 17.1 CH₂p-C₆H₄CF₃. MS mrz : 825.1

M – PF₆, 593.1

Cp dppe RuCO

Cp dppe Ru . Anal. Calcd. for C₄₇H₄₀F₉P₃Ru: C,

565.1

58.21; H, 4.16; Anal. Found: C, 58.30; H, 4.39. Spec-

3.6. Preparation of cyclopropenyl complexes

troscopic data of Cp dppe Ru5C5C Ph CH₂1-

C₁₀H₇PF₆5f : H NMR CDCl₃: 7.80–6.50 m,

Ph , 5.53 s, 5H, Cp , 3.20–2.90 m, 4H, CH₂, 2.98 s,

To a 15 ml acetone solution of complex 5a 0.50 g,

P NMR CDCl₃: 77.40. ¹³C

Ž .

2H, CH₂1-C₁₀H₇

0.60 mmol an aliquot of n-Bu NOH 10 ml was

NMR CDCl₃: 343.6 t, J_{C – P}s10.2 Hz, C , 136.1–

added. The mixture was stirred at room temperature for

1 h to give a bright yellow solution and then the solvent

was removed under vacuum. To the residue, 15 ml of

CH₃CN was added and the yellow precipitates was

filtered.

Ž ^a

125.4 m, Ph and C_b, 91.7 Cp , 30.8 CH₂1-C₁₀H₇

28.2 d, CH₂, J_{C – P}s14.1 Hz . MS mrz : 807.1

M – PF₆, 593.1

Cp dppe Ru . Anal. Calcd. for C₅₀H₄₃F₆P₃Ru: C,

Cp dppe RuCO

565.1

63.09; H, 4.55; Anal. Found: C, 63.24; H, 4.72.

The solid residue was further washed with 2=20 ml

of hexane and 2=20 ml of CH₃CN and dried under

vacuum to give the product identified as

3.4. Preparation of 5g

, 7a 0.30 g, 0.42 mmol in

72% yield. Spectroscopic data of 7a: ¹H NMR

20 ml CHCl₃solution of complex

Cp dppe RuC[CPh 0.30 g, 0.45 mmol , an aliquot of

CD₃COCD₃: 7.80–6.30 m, Ph , 4.95 s, 5H, Cp ,

3.80–3.50 m, 4H, PCH₂, 2.13 s, H, CHCN . ³¹P

BrCH₂CO₂CH₃142 ml, 1.5 mmol was added. The

solution was heated to reflux for 24 h. Then the solvent

was removed under vacuum and 20 ml of ether was

added and the slurry was filtered. These solids were

washed with 20 ml of hexane and 20 ml of ether and

dried under vacuum to give the product

NMR CDCl₃: 90.14, 88.47 two doublet with J_{P – P}

24.3 Hz . C NMR CDCl₃: 134.5–126.0 m, Ph ,

124.6 CN , 84.1 Cp , 32.9, 29.1 d, 2 PCH₂, 6.2

q 1 ,

C H CN . M S

m r z : 706.1

593.1 Cp dppe RuCO , 565.1 Cp dppe Ru . Anal.

Calcd. for C₄₁H₃₅NP₂Ru: C, 69.87; H, 5.01; N, 1.99;

Anal. Found: C, 69.64; H, 4.87; N, 1.79. Complexes 7b,

7c, 7d, 7e and 7f were similarly prepared. Spectroscopic

. Ž .

Cp dppe Ru5C5C Ph CH₂CO₂CH₃Br , 5g 0.35 g

in 94% yield. Spectroscopic data of 5g: ¹H NMR

CDCl₃: 8.00–6.50 m, Ph , 5.65 s, 5H, Cp , 3.50–

7b : ¹H NMR

3.00 m, 4H, CH₂, 3.49 s, 3H, CH₃, 2.35 s, 2H,

data of

CH₂. P NMR CDCl₃: 76.86. C NMR CDCl₃:

CDCl₃: 8.00–6.30 m, Ph , 4.70 s, 5H, Cp , 3.00–

2.30 m, 4H, PCH₂, 2.90 s, 1H, CHC₆F₅. ³¹P NMR

349.8 t, J_{C – P}s16.1 Hz, C_a, 172.5 CO₂, 135.6–

125.3 Ph , 123.6 C_b, 92.9 Cp , 51.7 CH₂CO₂,

CDCl₃: 91.15, 88.45 two doublet with J_{P – P}26.7 Hz .

C NMR CDCl₃: 144.4–117.3 m, Ph , 83.2 Cp ,

29.3 OCH₃, 27.6 d, CH₂CH₂, J_{C – P}s30.1 Hz . MS

mrz : 739.1 M –PF₆_q, 593.1 Cp dppe RuCO

28.8 dd, CH₂, J_{C – P}s 32.3 Hz, J_{C – P}s 15.1

565.1

C p dppe R u .

A nal. C alcd. for

Hz ,26.7 dd, CH₂, J_{C – P}s34.7 Hz, J_{C – P}s15.8 Hz ,

C₄₂H₃₉BrO₂P₂Ru: C, 61.62; H, 4.80; Anal. Found: C,

61.44; H, 4.56. Complex 5g^Xis also prepared by carry-

ing out the reaction at room temperature. The yield

19.1 CHC₆F₅. MS mrz : 847.2 M q1 , 593.2

Cp dppe RuCO , 565.2 Cp dppe Ru . Anal. Calcd.

for C₄₆H₃₅F₅P₂Ru: C, 65.32; H, 4.17; Anal. Found: C,

76% is lower.

65.47; H , 4.34. Spectroscopic data of

7c : H NMR CDCl₃:

(

)

( )

3.5. Formation of Cp dppe RUCOCH₂Ph 6 from 5g

7.50–6.60 m, Ph , 4.66 s, 5H, Cp , 3.40–2.90 m, 4H,

CH₂, 2.75 s, 1H, CHC₆H₅. ³¹P NMR CDCl₃:

Complex 5g^X0.30 g, 0.36 mmol , prepared at room

91.58, 90.18 two doublet with J_{P – P}25.5 Hz . ¹³C NMR

temperature, was dissolved in 20 ml of CHCl₃and

CDCl₃: 135.9–122.3 m, Ph , 83.2 Cp , 27.3, 26.7

NH₄PF₆0.30 g was added. And the solution was

CH₂CH₂, 30.4 CHC₆H₅. MS mrz : 756.1 M

(

)

424

C.-W. Chang et al.rJournal of Organometallic Chemistry 553 1997 417–425

q1 , 593.1 Cp dppe RuCO , 565.1 Cp dppe Ru .

mmol in 10 ml CHCl₃. This mixture was stirred at

Anal. Calcd. for C₄₆H₄₀P₂Ru: C, 73.10; H, 5.33; Anal.

Found: C, 73.22; H, 5.47. Spectroscopic data of

room temperature for 48 h to give orange red precipitate

which was filtered off, washed with 10 ml of acetone

and 2=10 ml of hexane, then dried in vacuo yielding

7d : ¹H NMR

. Ž

CDCl₃: 7.80–6.20 m, Ph , 4.56 s, 5H, Cp , 3.40–

Ru 5C5C Ph CH CN ₂I₂9a 0.13 g, 39% yield .

3.20 m, 4H, CH₂, 2.60 s, 1H, CH p-C₆H₄CN . ³¹P

Complex 9a is insoluble in common organic solvents

except DMSO. Spectroscopic data of 9a : ¹H

NMR CDCl₃: 90.54, 89.54 two doublet with J_{P – P}

24.3 Hz . C NMR CDCl₃: 134.3–125.6 m, Ph and

NMR CDCl₃: 7.40–6.80 m, Ph , 5.30 s, 10H, Cp ,

3.20–2.60 m, 8H, CH₂, 2.48 s, 2H, CHCN . ³¹P

C_a, 120.62 CN , 83.0 Cp , 27.4, 27.3 CH₂_qCH₂,

32.3 CH p-C₆H₄CN . MS mrz : 847.2 M q1 ,

NMR CDCl₃: 76.34, 75.28 two doublet with J_{P – P}

593.2 Cp dppe RuCO , 565.2 Cp dppe Ru . Anal.

Calcd. for C₄₇H₃₉NP₂Ru: C, 72.29; H, 5.03; Anal.

Found: C, 72.31; H, 4.89. Spectroscopic data of

19.5 Hz . C NMR CDCl₃: 343.5 t, J_{C – P}s15.0 Hz,

C_a, 131.5–129.3 m, Ph , 93.2 Cp , 26.9, 25.0

CH₂CH₂, 24.3 CHCN . MS mrz : 1537.3 M –

7e : ¹H NMR

I₅, 1409.4 M q1-2I₃, 565.3 Cp dppe Ru

CDCl₃: 8.02–6.22 m, Ph , 4.64 s, 5H, Cp , 3.00–

3.9. X-ray analysis of 2, 3, 6, and 7b

³¹P

NMR CDCl₃: 91.03, 89.82 two doublet with

2.30 m, 4H, CH₂, 2.19 s, 1H, CH p-C₆H₄CF₃

Single crystals of 2 suitable for an X-ray diffraction

study were grown as mentioned above. A single crystal

of dimensions 0.20=0.30=0.50 mm³was glued to a

glass fiber and mounted on an Enraf–Nonius CAD4

diffractometer. Initial lattice parameters were deter-

mined from a least-squares fit to 25 accurately centered

reflections. Cell constants and other pertinent data are

collected in Table 1. Data were collected using the

ur2u scan method. The final scan speed for each

reflection was determined from the net intensity gath-

ered during an initial prescan and ranged from 2 to 78

min^y1. The scan angle was determined for each reflec-

tion according to the equation 0.8q0.35=tan u.

J_{P – P}25.5 Hz . C NMR CDCl₃: 144.3–123.7 m,

Ph , 83.2 Cp , 28.7 dd, CH₂CH₂, J_{C – P}s33.9 Hz,

J_{C – P}s16.0 Hz , 26.8 dd, CH₂CH₂, J_{C – P}s29.0

Hz, J_{C – P}s15.7 Hz , 13.6 CH p-C₆H₄CF₃. MS

mrz : 825.2 M q1 , 593.2 Cp dppe RuCO ,

565.2 Cp dppe Ru . Anal. Calcd. for C₄₇H₃₉F₃P₂Ru:

C, 68.52; H, 4.77; Anal. Found: C, 68.35; H, 4.67.

Spectroscopic data of

7f : H NMR CDCl₃: 8.10–6.40 m, Ph , 4.63 s, 5H,

Cp , 3.00–2.30 m, 4H, CH₂, 1.98 s, 1H, CH 1-

Ž . Ž

P NMR CDCl₃: 91.39, 90.17 two doublet

C₁₀H₇

with J_{P – P}s25.5 Hz . C NMR CDCl₃: 135.2–122.3

m, Ph , 83.2 Cp , 24.1 CH 1-₁₀H₇, 28.1, 27.0

The raw intensity data were converted to structure

factor amplitudes and their esd’s by correction for scan

speed, background and Lorentz, polarization effects. An

empirical correction for absorption based on the az-

imuthal scan, was applied to the data set. Crystallo-

graphic computations were carried out on a Microvax

III computer using the NRCC structure determination

package 40 . Merging of equivalent and duplicate re-

flections gave a total of 4597 unique measured data

from which 2839 were considered observed, I)2.0

Ž . Ž .

MS m r z : 807.1 M q 1 , 593.1

q q

CH₂CH₂

Cp dppe RuCO , 565.1 Cp dppe Ru . Anal. Calcd.

for C₅₀H₄₂P₂Ru: C, 74.52; H, 5.25; Anal. Found: C,

74.22; H, 5.03.

[[

]

(

)

(

)

]

3.7. Synthesis of Ru 5C5C Ph CH C₆F₅HgCl Cl

(

)

To a mixture of 7b 0.20 g, 0.24 mmol , and HgCl₂

0.076 g, 0.28 mmol at room temperature, 15 ml of

CH₂Cl₂was added by syringe. The mixture was stirred

under nitrogen for 5 min. The work-up procedure was

the same as that in 5b. The product 8b was obtained

Ž .

s I . The structure was first solved by using the heavy

atom method Patterson synthesis which revealed the

position of metal, then refined via standard least-squares

0.21 g, 86%

and w as identified as

and difference Fourier techniques. The quantity mini-

Cp dppe Ru5C5C Ph CH C₆F₅HgCl ^qCl^y. Spectro-

.Ž

mized by the least squares program was w F_oy F

scopic data of 8b: H NMR CDCl₃: 7.67–6.60 m,

Ph , 5.59 s, 5H, Cp , 3.40–2.90 m, 4H, CH₂, 3.38 s,

The analytical forms of the scattering factor tables for

the neutral atoms were used 41 . All other non-hydro-

gen atoms were refined by using anisotropic thermal

parameters. Hydrogen atoms were included in the struc-

ture factor calculations in their expected positions on

the basis of idealized bonding geometry but were not

refined in least squares. Final refinement using full-ma-

trix, least squares converged smoothly to values of

Rs0.039 and R_ws0.038. Final values of all refined

1H, CHHgCl . P NMR CDCl₃: 78.59, 78.10 two

doublet with J_{P – P}s18.2 Hz . ¹³C NMR CDCl₃:

133.0–127.0 m, Ph and C_b, 92.1 Cp , 47.7 s, H,

CHHgCl , 28.8, 27.7 d, CH₂CH₂, J_{C – P}s15.9 Hz .

MS mrz : 1083.1 M –Cl , 593.2 Cp dppe RuCO ,

565.2 Cp dppe Ru

3.8. Dimerization of 7a in the presence of allyl iodide

atomic positional parameters with esd’s and tables of

thermal parameters, and structure factors are given in

the supporting information.

Excess freshly distilled allyl iodide 0.65 ml, 7.1

mmol was added to a solution of 7a 0.20 g, 0.28

(

)

C.-W. Chang et al.rJournal of Organometallic Chemistry 553 1997 417–425

425

14 R. Gompper, E. Bartmann, Angew. Chem., Int. Ed. Engl. 24

The procedures for 3, 6, and 7b were similar. The

final residues of the refinement were Rs0.054, R_ws

0.064 for 3; Rs0.049, R_ws0.056 for 6; and Rs

0.053, R_ws0.050 for 7b. Final values of all refined

1985 209.

15 U. Kirchgassner, H. Piana, U. Schubert, J. Am. Chem. Soc. 113

1991 2228.

16 S. Miki, T. Ohno, H. Iwasaki, Z.I. Yoshida, J. Phys. Org. Chem.

atomic positional parameters with esd’s and tables of

thermal parameters and structure factors are given in the

supporting information.

1 1988 333.

17 Z.I. Yoshida, Pure Appl. Chem. 54 1982 1059.

18 R.R. Schrock, Acc. Chem. Res. 19 1986 342.

19 R.P. Hughes, J.W. Reisch, A.L. Rheingold, Organometallics 4

1985 1754.

3.10. Supporting information aÕailable

20 R.P. Hughes, W. Klaui, J.W. Reisch, A. Muller, A.L. Rhein-

gold, Organometallics 4 1985 1761.

Details of the structural determination for complexes

2, 3, 6, and 7b including tables of crystal data and

structure refinement, positional and anisotropic thermal

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