Bimetallic complexes: V.1 Synthesis and reactions of C5H4PPh2-bridged zirconium-rhenium complexes

DOI: 10.1016/S0022-328X(97)00583-4

Source and publish data:

Journal of Organometallic Chemistry p. 91 - 98 (1998)

Update date:2022-07-29

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Authors:

Gutmann, Thomas

Dombrowski, Eberhard

Burzlaff, Nicolai

Schenk, Wolfdieter A.

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Article abstract of DOI:10.1016/S0022-328X(97)00583-4

Bimetallic Zr-Re complexes with bridging C₅H₄PPh₂ ligands (henceforth abbreviated as Cp′) are accessible from the mononuclear zirconocene dichloride Cp′₂ZrCl₂ (1) and reactive rhenium complexes. The attempted synthesis of a cationic complex from 1 and [Re(CO)₃(NCMe)₃]BF₄ resulted in the formation of the zirconium-free compound [ReCl(CO)₃(C₁₀H₁₀(PPh₂) ₂)] (2). 2 is apparently formed by cleavage of the Cp′-Zr bonds followed by intramolecular Diels-Alder addition. The compound was fully characterized including an X-ray crystal structure determination of the CDCl₃ solvate (triclinic, space group P1 (No. 2), a=945.1(5) pm, b=1113.9(6) pm, c=1888.5(10) pm, α=92.36(3)°, β=89.98(3)°, γ=113.49(2)°, V=1.821(2)×10⁹ pm³, Z=2). 1 and the highly reactive 'salt' [Re(CO)₅FBF₃] give the mono-bridged ionic complex [Cp′Cl₂Zr(μ-Cp′)Re(CO)₅]BF₄ (3). The doubly Cp′-bridged complex [Cp′₂Cl₂ZrReCl(CO)₃] (4) may be obtained from 1 and either [Re(CO)₅Cl] or, more cleanly, [Re₂(μ-Cl)₂(CO)₆(THF)₂]. Reaction of 4 with a stoichiometric amount of LiAlH₄ gives the bridging hydride complex [Cp′₂ClZr(μ-H)ReH(CO)₃] (5). From 5 and NaSMe the analogous methyl thiolate complex 6 was obtained in an NMR tube experiment. Reduction of 4 using sodium amalgam produces the dark blue-green complex [Cp′₂ClZr-Re(CO)₃] (7) which contains a direct Zr-Re bond. Addition of HCl across this polar metal-metal bond gives two isomeric hydrides [Cp′₂Cl₂ZrReH(CO)₃] (8a, b) in a 1:1 ratio and with fac and mer coordination geometries around rhenium, respectively.

Full text of DOI:10.1016/S0022-328X(97)00583-4

Journal of Organometallic Chemistry 552 1998 91–98

Bimetallic complexes

V. Synthesis and reactions of C₅H₄PPh₂-bridged zirconium-rhenium

complexes

)

Thomas Gutmann, Eberhard Dombrowski, Nicolai Burzlaff, Wolfdieter A. Schenk

Institut fur Anorganische Chemie der UniÕersitat Wurzburg, Am Hubland, Wurzburg D-97074, Germany

Received 12 June 1997

Abstract

Bimetallic Zr–Re complexes with bridging C₅H₄PPh₂ligands henceforth abbreviated as Cp are accessible from the mononuclear

Ž .

zirconocene dichloride Cp^X₂ZrCl₂

. Ž . x

and reactive rhenium complexes. The attempted synthesis of a cationic complex from 1 and

. Ž . .x Ž .

Re CO NCMe BF₄resulted in the formation of the zirconium-free compound ReCl CO C₁₀H₁₀PPh₂2 . 2 is apparently

formed by cleavage of the Cp^X–Zr bonds followed by intramolecular Diels–Alder addition. The compound was fully characterized

Ž .

including an X-ray crystal structure determination of the CDCl₃solvate triclinic, space group P1 No. 2 , as945.1 5 pm,

Ž .

. x

bs1113.9 6 pm, cs1888.5 10 pm, as92.36 3 8, bs89.98 3 8, gs113.49 2 8, Vs1.821 2 =10 pm , Zs2 . 1 and the highly

Ž .

reactive ‘salt’ Re CO FBF₃give the mono-bridged ionic complex Cp Cl₂Zr m-Cp Re CO BF₄3 . The doubly Cp -bridged

⁵Ž . x Ž .

. Ž . Ž

. x

complex Cp₂Cl₂ZrReCl CO

may be obtained from 1 and either Re CO Cl or, more cleanly, Re₂m-Cl CO THF

Reaction of 4 with a stoichiometric amount of LiAlH₄gives the bridging hydride complex Cp₂ClZr m-H ReH CO

NaSMe the analogous methyl thiolate complex 6 was obtained in an NMR tube experiment. Reduction of 4 using sodium amalgam

. x Ž .

5 . From 5 and

. x Ž .

produces the dark blue-green complex Cp₂ClZr-Re CO

7 which contains a direct Zr–Re bond. Addition of HCl across this polar

. x Ž

metal–metal bond gives two isomeric hydrides Cp₂Cl₂ZrReH CO

around rhenium, respectively. q 1998 Elsevier Science S.A.

8a, b in a 1:1 ratio and with fac and mer coordination geometries

Keywords: Bimetallic complexes; Hydride; Metal–metal bonds; Rhenium; Zirconium

Ž .

new types of reactions: a Cationic compounds isoelec-

tronic to the known zirconium–tungsten complexes 2

should readily undergo nucleophilic addition at either

the rhenium atom itself or at a rhenium-bound carbonyl

1. Introduction

w x

In our previous work on C₅H₄PPh₂-bridged binu-

clear complexes 1–3 we have described several at-

tempts to construct reactive species which would rapidly

add and transform small, polar substrate molecules. The

Ž .

group; b Zr IV –Re I complexes should be readily

Ž .

reducible to metal–metal bonded Zr III –Re 0 com-

pounds which in turn might be expected to undergo

1,2-addition reactions.

Ž .

various approaches included a ligand addition to M–

m-Cl –M -bridged complexes MsTi, Zr; M sMo,

w x Ž .

2 , b coupling of zirconium-bound methyl groups

with tungsten-bound nitrile ligands 3 , and c addition

w x Ž .

Ž .

and insertion reactions of binuclear zirconium II cyclo-

hexyne complexes 1 . It was hoped that an extension of

this work to include binuclear zirconium–rhenium com-

plexes might open up further opportunities to discover

w x

2. Results and discussion

At room temperature, tris acetonitrile tricarbonylrhe-

w x

nium-tetrafluoroborate

did not react with

)

bis diphenyl-phosphinocyclopentadienyl zirconium

dichloride 1 5 . Upon prolonged heating to 808C a

Corresponding author.

Ž . w x

w x

For Part III, see Ref. 1 .

0022-328X

(

)

T. Gutmann et al.rJournal of Organometallic Chemistry 552 1998 91–98

slow reaction could be observed, the only isolable prod-

uct, however, was the mononuclear complex 2 which

obviously resulted from Zr–Cp^Xbond cleavage followed

by Diels–Alder dimerization of the two cyclopentadi-

Ž ..

enyl groups Eq. 1 . Similar observations were made

w x

6 or

when norbornadiene tetracarbonylrhenium

w x

mesitylene tricarbonylrhenium salts 7 were used in-

stead.

Fig. 1. Molecular structure and partial atomic numbering scheme for

. Ž . .x Ž .

ReCl CO C₁₀H₁₀PPh₂2 .

which is readily obtained in situ from Re CO CH₃

and HBF₄10–12 , upon reaction with 1 gave the

Ž ..

mono-bridged binuclear complex 3 Eq. 2 in quantita-

tive yield.

Ž .

Compound 2 is an off-white crystalline compound

which is readily soluble in all common organic solvents

except aliphatic hydrocarbons. Its H-NMR spectrum is

. Ž

very similar to those of the analogous M CO MsCr,

Mo complexes 8,9 . The two phosphorus nuclei are

nonequivalent and give two widely separated doublet

resonances in the ³¹P-NMR spectrum. Unambiguous

proof of the identity of 2 came from a X-ray structure

determination of the CDCl₃solvate Fig. 1 .

The coordination geometry of the Re atom is almost

perfectly octahedral. The Re–Cl and Re–P distances are

Ž .

within the normal range, the Re–C 1 bond trans to the

Ž .

Cl ligand is, as expected, distinctly shorter than Re–C 2

Ž .

and Re–C 3 , trans to P Table 1 . The P 1 –Re–P 2

Ž .

angle is only slightly larger than the P–Mo–P angle in

. w x

the analogous molybdenum complex 89.48 8 , and

even the tricyclic C₁₀skeletons of the two compounds

are almost superimposable.

2 may well arise from the decomposition of a binu-

clear Zr–Re complex which, unexpectedly, was too

unstable to survive the relatively harsh reaction condi-

tions. Thus, a more reactive source of coordinatively

unsaturated rhenium carbonyl cations had to be sought.

3 is a colourless crystalline compound which is

soluble only in polar organic solvents. Its infrared spec-

Ž .

trum in the n CO region exhibits the typical pattern of

a cationic Re CO complex. The ³¹P-NMR spectrum of

3 consists of two singlets, one with a chemical shift

close to that of 1 and the other one slightly downfield at

y5.0 ppm which is typical of a Re-bound PPh₂R

Ž .

ligand Table 2 .

Indeed, the weakly coordinated ‘salt’ Re CO FBF₃

(

)

T. Gutmann et al.rJournal of Organometallic Chemistry 552 1998 91–98

Table 1

Selected bond distances pm and angles

. .x

was attempted. Thus, Re CO Cl was converted to a

Ž .

for ReCl CO

w x

binuclear ‘ Re CO Cl equivalent’ 13 which reacts

C₁₀H₁₀PPh₂

)CDCl₃2)CDCl₃

Ž ..

with 1 to give 4 in quantitative yield Eq. 4 .

Ž .

Re–Cl 1

Re–P 1

Ž .

249.7 2

248.7 2

Ž .

85.84 6

Ž .

94.10 6

173.11 12

88.93 12

86.82 12

91.05 5

95.91 12

Cl 1 –Re–P 1

Ž .

Cl 1 –Re–P 2

Ž .

Ž . Ž .

Re–P 2

249.6 2

Cl 1 –Re–C 1

Ž .

Ž . Ž .

Re–C 1

190.9 4

Cl 1 –Re–C 2

Ž . Ž .

Ž .

Re–C 2

193.9 4

Cl 1 –Re–C 3

Ž . Ž .

Ž .

P 1 –C 11

Ž .

Re–C 3

194.5 4

P 1 –Re–P 2

Ž .

Ž . Ž .

183.3 4

P 1 –Re–C 1

Ž .

Ž . Ž .

91.27 12

P 1 –C 21

182.7 4

P 1 –Re–C 2

Ž . Ž .

Ž .

172.27 11

P 1 –C 50

183.9 4

P 1 –Re–C 3

Ž . Ž .

Ž .

92.48 12

P 2 –C 31

182.9 4

P 2 –Re–C 1

Ž .

Ž . Ž .

176.25 12

P 2 –C 41

182.6 4

P 2 –Re–C 2

Ž .

Ž . Ž .

P 2 –C 57

181.0 4

P 2 –Re–C 3

Ž . Ž .

86.78 12

Ž .

84.4 2

Ž .

91.6 2

Ž .

91.3 2

Ž . Ž .

Ž .

C 1 –O 1

112.5 5

C 1 –Re–C 2

Ž . Ž .

Ž .

C 2 –O 2

114.3 5

C 1 –Re–C 3

Ž . Ž .

Ž .

Ž . Ž .

C 3 –O 3

113.3 5

C 2 –Re–C 3

Any attempt to convert 3 into a doubly bridged

complex failed. UV irradiation or reaction with Me₃NO

gave only intractable product mixtures. A doubly bridged

neutral complex, however, was obtained upon refluxing

Ž ..

a mixture of 1 and Re CO Cl in benzene Eq. 3 .

The expected compound 4 could be isolated in 62%

yield, a major side product being the ‘Cp-dimer’ com-

plex 2. 4 is a colourless crystalline compound which is

readily soluble in chlorinated hydrocarbons and THF.

Its IR spectrum exhibits the typical three-band pattern

of fac- ReXL₂CO complexes, similar to that of 2. A

singlet in the ³¹P-NMR spectrum indicates that the two

phosphorus nuclei are equivalent.

Ž .

Although 4 seemed to be a fairly stable compound,

surprising difficulties were encountered upon attempting

substitution reactions. Thus, treatment of 4 with either

Ž .

LiCH₃, Al₂CH_{3 6}, NaSCH₃, or KOt–Bu, even under

mild conditions, gave mainly the zirconium-free

mononuclear complex 2 and none of the desired ex-

change products. Careful addition of a stoichiometric

amount of LiAlH₄in THF, however, produced a small

Since 4 is thermally labile—upon heating in toluene

rapid decomposition to 2 occurs—a milder synthesis

(

)

T. Gutmann et al.rJournal of Organometallic Chemistry 552 1998 91–98

Table 2

The infrared spectrum of 5 in the n CO region

exhibits two bands of unequal intensity but in the same

frequency range as other tricarbonyl hydride complexes

Spectroscopic data of the binuclear Zr–Re complexes 3–8

Number IR n CO ¹H-NMR^aCp

Re–H

³¹P-NMR PPh₂

Ž .^b

Ž .^c

2153 w

5.50 to 6.50 m

y12.7 s

of rhenium 14 . This indicates that 5 is a neutral

tricarbonyl with a geometry distinctly distorted from

octahedral. The two equivalent phosphorus nuclei give

rise to a singlet in the ³¹P-NMR spectrum downfield

from that of the starting compound 4. Two hydride

Ž .

2043 s

9.5 s

1988 m

Ž .^d

Ž .^e

y1.9 s

2036 s

6.39 m

Ž .

1961 s

Ž .

6.76 m

1916 s

6.84 m

triplets are observed in the H-NMR spectrum which

collapse to singlets upon phosphorus decoupling. At

first sight it seems unusual that no coupling is observed

between the two nonequivalent hydride ligands. How-

ever, it is well-known that in second- and third-row

complexes there is a sign change between cis and trans

Ž .^h

y4.56 t

Ž .^g

6.95 s

2007 m 5.42 m

Ž .^h

y7.16 t

1931 vs 5.50 m

5.54 m

6.45 m

Ž .^h

Ž .^g

7.55 s

5.35 m

y6.02 t

Ž .^k

y7.70 t

5.45 m

couplings. The situation is particularly well-documented

5.72 m

for phosphine complexes where J cis is negative and

6.39 m

J trans is positive 15–20 . It is, therefore, not too

surprising that at an intermediate H–Re–H angle in a

Ž .^l

1992 w

Ž .^g

4.26 m

10.6 s

Ž .

1912 s

4.71 m

formally seven-coordinate structure J H–H should as-

sume a value close to zero. Indeed, similar Zr–Ru

complexes with bridging C₅Me₄PMe₂, Cl, and H lig-

ands have recently been synthesized which were found

to have also very small H–H couplings between bridg-

Ž .

1891 s

6.23 m

6.35 m

Ž .ⁿ

y3.98 t

Ž .^g

2014 m 5.93 m

11.2 s

Ž .

1928 s

5.99 m

1905 m 6.51 m

ing and terminal hydrides 21,22 .

6.94 m

Ž .^o

y5.55 d

Ž .^p

2031 m 6.21 m

8.2 d

Ž .

Ž .^p

1946 s

6.36 m

9.0 d

6.52 m

6.56 m

^aAryl signals in the 6.5–8.0 ppm region are uncharacteristic and have

been omitted.

^bCH₂Cl₂. ^cCD₂Cl₂. ^dCHCl₃. ^eCDCl₃. ^fNujol. ^gC₆D₆. J P–H s

15 Hz. ⁱ2.37 s, SCH₃

J P–H s17 Hz. ^lC₆H₆. ^mC₆H₅CH₃.

J P–H s27 Hz. J P–H s25 Hz. J P–P s22 Hz.

Ž ..

quantity of the dihydride 5 Eq. 5 along with some

insoluble materials.

Ž .

Evidence that in the hydride transfer reaction Eq.

Ž ..

one chloride ligand is retained at zirconium comes

from the following experiment Eq. 6 . A small quan-

Ž ..

tity of 5 was treated in THF with an excess of NaSMe

and the C₆D₆soluble part examined by H- and ³¹P-

Ž .

NMR. Clean spectra were obtained which exhibited

slightly shifted P and hydride signals Table 2 . A

(

)

T. Gutmann et al.rJournal of Organometallic Chemistry 552 1998 91–98

Ž ..

new singlet at 2.37 ppm in the correct intensity ratio is

7 Eq. 7 . It is advisable to monitor the progress of the

reaction by IR spectroscopy and separate the solution

from excess amalgam as soon as the starting compound

4 is consumed completely. Otherwise, overreduction to

a brown intractable mixture occurs. 7 can be isolated in

good yield from a benzene solution by freeze-drying.

typical of a Zr-bound SMe group 1–3 .

The IR spectrum of 7 exhibits three n CO bonds at

distinctly lower frequencies compared to 4, consistent

with a change in the formal oxidation state of the

rhenium atom from qI to zero. Furthermore, there is a

conspicuous change in relative band intensities which

means that two of the three CO ligands form a quite

large OC–Re–CO angle. Obviously, the coordination

geometry around the rhenium atom is severely distorted

from a regular octahedron as a result of the constraints

imposed by the zirconium–rhenium bond.

It was hoped that the addition of dihydrogen to 7

would provide a cleaner access to the dihydride com-

plex 5. However, no reaction occurred at room temp. up

to a pressure of 50 bar. At higher temperatures complete

decomposition was observed, mainly to the inescapable

mononuclear compound 2. Similarly, attempted nucleo-

philic substitution reactions with SMe^y, Ot-Bu^y, ligand

additions with isonitriles, alkynes, or 1,2- additions of

aldehydes, methyl iodide or iodine resulted in decompo-

sition to untractable materials.

Ž .

Careful reduction of 4 using sodium amalgam pro-

duces the dark blue-green metal–metal bonded complex

Ž .

Gaseous HCl, however, was cleanly added giving a

1:1 mixture of two isomeric monohydride complexes

8a, b Eq. 8 . In 8a the two phosphorus nuclei are

sharpens to a singlet upon phosphorus decoupling. The

P H -NMR spectrum consists of a clean AB system;

Ä¹

Ž ..

with off-resonance decoupling such that the hydride

equivalent Table 2 , and consequently the hydride sig-

nal is split into a regular triplet. This isomer certainly

has a fac-octahedral structure similar to that of fac-

region remains coupled the signal at 8.2 ppm changes

into a doublet of doublets. Thus, it is clear that in 8b the

hydride ligand is coupled to only one of the two phos-

phorus nuclei. Surprisingly, complexes of the type mer-

.Ž

x w

ReH dppe CO

23 . Of the five observable n CO

absorptions those at 2014, 1928 and 1905 cm^y1may be

attributed to this isomer. The second isomer 8b gives

only a doublet signal in the hydride region which

ReH R₂PLPR₂CO to be compared with 8b have,

.Ž

. x

to our knowledge, not yet been described. Complexes

. Ž ₃x

mer- ReH PR₃CO

with monodentate phosphines

(

)

T. Gutmann et al.rJournal of Organometallic Chemistry 552 1998 91–98

adopt a trans- PR₃geometry 14–18,20 . However,

H-NMR 400 MHz, CD₂Cl₂: ds0.79, 1.89, 1.90,

there are a few examples of poly phosphine -hydride

complexes of rhenium which seemingly have two fea-

2.38, 2.92, 2.93, 3.42, 5.52, 6.14 m, C₁₀H₁₀, 7.1–7.9

m, Ph . P-NMR 162 MHz, CD₂Cl₂: dsy10.1,

Ž .

.Ž

tures in common:

J P–H trans is distinctly

2.5 AB-system, J AB s28 Hz . Anal. found: C,

.Ž

Ž .

smaller than J P–H cis , and b isomers, although

56.38; H, 3.92. C₃₇H₃₀ClO₃P₂Re 806.25 calcd.: C,

55.12; H, 3.75.

often in thermodynamic equilibrium, do not interconvert

on the NMR timescale 24–26 . Thus, it is perfectly

reasonable to assume a slightly distorted mer-octahedral

[

(

)

(

) ] ( )

4.2. Cp Cl₂Zr m-Cp Re CO ₅BF₄3

structure for 8b. This would also explain the remaining

w x

23 , a weak

n CO bands at 2031 and 1946 cm

To a solution of Re CO Me 51 mg, 0.15 mmol in

feature at 1815 cm^y1may be ascribed to overlapping

dichloromethane 5.0 ml an equimolar amount of

n Re–H absorptions of both isomers.

HBF₄)Et₂O is added. Within 2 h Re CO FBF₃sepa-

rates as colorless crystals 12 which are washed with

Ž .

dichloromethane and dried under vacuum. Cp^X₂ZrCl₂

3. Conclusions

100 mg, 0.15 mmol an dichloromethane 5.0 ml are

added and stirred for 15 min. The product is isolated

after filtration by partial evaporation and addition of

pentane. Yield 145 mg 93% , colorless microcrystalline

The assembly of binuclear zirconium–rhenium com-

plexes with bridging C₅H₄PPh₂ligands rests on the use

of highly reactive mononuclear rhenium complexes ca-

pable of undergoing ligand exchange under mild condi-

tions. A severely limiting factor is the unexpected labil-

ity of the Zr-C₅H₄PPh₂linkage. Nevertheless, reduced

complexes with Zr–Re and Re–H bonds are accessible

under carefully controlled conditions and might pave

the way to a further development of this chemistry.

powder, m.p. 1048C dec. . Anal. found: C, 44.36; H,

2.58. C₃₉H₂₈BCl₂F₄O₅P₂ReZr 1073.74 calcd.: C,

43.63; H, 2.63.

[

(

) ] ( )

4.3. Cp₂ZrCl₂ReCl CO ₃

A suspension of Cp^X₂ZrCl₂

Ž .

Ž . Ž

1 0.43 g, 0.65

mmol and Re CO Cl 0.23 g, 0.65 mmol in benzene

10 ml is heated under reflux for 15 min. The solution

4. Experimental section

is filtered and evaporated to 3 ml whereupon 4 separates

as an almost colorless crystalline powder. The filtrate

contains a mixture of 4 and 2 which can be completely

converted to 2 by prolonged heating. Yield 0.39 g

All manipulations were carried out in Schlenk-type

glassware under an atmosphere of purified nitrogen or

argon. Solvents were dried and distilled under nitrogen

prior to use. NMR solvents were degassed and stored

under nitrogen over molecular sieves. NMR: Bruker

62% , m.p. 1158C dec. . Anal. found: C, 45.63; H,

3.03. C₃₇H₂₈Cl₃O₃P₂ReZr 966.37 calcd.: C, 45.99;

H, 2.92.

Ž .

AMX 400; chemical shifts are reported in ppm vs. TMS

Re CO Cl 0.11 g, 0.30 mmol is refluxed in

Ž³¹

¹H, C and 85% H₃PO₄

P . IR: Bruker IFS 25,

THF 10 ml overnight whereby it is completely con-

verted to Re₂m-Cl CO THF

. Ž . Ž

x w Ž .

Perkin–Elmer 283.

The following starting materials were prepared by

Ž . w x

13 . Cp₂ZrCl₂1

0.20 g, 0.30 mmol is added and the mixture is stirred

published procedures: Cp^X₂ZrCl ₂

5 ,

for 30 min at 208C. 4 is isolated in quantitative yield

upon evaporation and addition of pentane.

4 ,

R e C O

N C M e

n o r b o r n a d i e n e B F ₄

B F

. Ž

w x

R e C O

. Ž

6 ,

x w

w x

12 ,

[

(

)

(

) ] ( )

Re CO mesitylene BF₄7 , Re CO FBF

4.4. Cp₂ClZr m-H ReH CO ₃

w Ž

⁵x w³

Re CO Cl

27 , Re CO Me

12 , Re₂m-

. Ž

x w

Cl THF CO

13 . All other reagents were used as

To a solution of 4 0.17 g, 0.18 mmol in THF 3.0

obtained commercially.

ml is added, at 08C, 4.0 ml of a 0.10 M solution of

LiAlH₄0.40 mmol in the same solvent. After the

mixture has been stirred overnight at 208C it is taken to

dryness and the residue extracted with benzene. Upon

[

(

) (

(

) )] ( )

4.1. ReCl CO ₃C₁₀H₁₀PPh₂2

A solution of Cp^X₂ZrCl₂0.10 g, 0.15 mmol and

evaporation 53 mg 33% of spectroscopically pure 5

. Ž

Re CO NCMe BF₄0.072 g, 0.15 mmol in CDCl₃

remain as colorless crystalline powder.

0.5 ml was heated to 808C and the reaction monitored

by ³¹P-NMR. Aside from a number of unidentified

decomposition products 2 was formed slowly as the

main component of the mixture. Solids were separated

by centrifugation and 2 was crystallized by addition of

[

(

) ] ( )

4.5. Cp₂ClZrRe CO ₃

To sodium amalgam, prepared from 1.0 ml of mer-

cury and 0.20 g of sodium, is added benzene 10 ml

hexane. Colorless crystalline powder, m.p. 1348C dec. .

and 4 0.35 g, 0.36 mmol . The mixture is repeatedly

(

)

T. Gutmann et al.rJournal of Organometallic Chemistry 552 1998 91–98

Table 4

degassed and flushed with argon and stirred vigorously

whereupon the solution turns blue-green. As soon as the

staring compound 4 is consumed to be checked by IR

the mixture is filtered over Celite and the product

isolated from the filtrate by freeze-drying. Yield 0.20 g

Atomic coordinates =10 and equivalent isotropic displacement

parameters pm =10

for 2)CDCl₃

Ž .

1828 1

Ž .

2059 1

3233 1

Ž .

8257 1

8200 1

7375 1

9528 2

8105 2

9438 2

7336 1

9039 2

8982 2

8175 2

8849 2

8999 2

9452 2

9770 2

9630 2

9169 2

8351 2

7827 2

7981 2

8648 3

9179 2

9026 2

6689 2

6286 2

Ž .

33 1

Ž .

33 1

P 1

Ž .

4680 1

1865 1

1819 4

y1710 3

1615 4

1719 1

1838 4

62% , green-black microcrystalline powder, m.p. 638C

Ž .

36 1

P 2

341 1

dec. . Anal. found: C, 49.63; H, 3.66.

Ž .

63 1

O 1

479 3

C₃₇H₂₈ClO₃P₂ReZr 895.46 calcd.: C, 49.63; H, 3.15.

Ž .

65 1

O 3

758 3

Ž .

82 1

O 2

Ž .

3966 3

Ž .

57 1

Cl 1

3568 1

[

(

) ] ( )

4.6. Cp₂Cl₂ZrReH CO ₃

Ž .

43 1

C 1

1030 4

Ž .

48 1

C 2

1723 4

y410 5

3303 4

Gaseous HCl is introduced for a few seconds into a

Ž .

C 11

Ž .

45 1

C 3

1230 4

solution of 7 0.30 g, 0.34 mmol in toluene 5.0 ml at

y708C. The mixture, which turns colorless immedi-

ately, is evaporated to dryness and the residue recrystal-

Ž .

5805 4

Ž .

36 1

2783 3

Ž .

41 1

C 12

5378 4

6278 5

7578 5

7993 5

7138 4

5308 4

5855 4

6261 5

6142 5

5579 5

5171 5

345 4

1477 3

Ž .

49 1

C 13

1108 4

Ž .

57 1

C 14

2030 4

lized from toluenerpentane. Yield 0.26 g 83% , color-

Ž .

58 1

C 15

3327 4

less microcrystalline powder. Anal. found: C, 47.60; H,

Ž .

48 1

C 16

3702 4

3.79. C₃₇H₂₉Cl₂O₃P₂ReZr 932.92 calcd.: C, 47.69;

H, 3.14.

Ž .

39 1

C 21

5002 3

Ž .

46 1

C 22

5897 3

Ž .

57 1

C 23

7217 4

Ž .

63 1

C 24

7671 4

4 .7 . X -ra y stru ctu re d eterm in a tio n o f

Ž .

60 1

C 25

6794 4

[

(

) (

(

) )]

(

)

ReCl CO ₃C₁₀H₁₀PPh₂

)CDCl₃2)CDCl₃

Ž .

49 1

C 26

5471 4

Ž .

44 1

C 31

y236 4

Ž .

84 5

Ž .

56 1

Clear colorless crystals of 2)CDCl₃were obtained

C 32

676 4

Ž .

C 33

y1019 5

260 5

5749 2

5614 2

66 1

71 1

from a NMR sample of 2. 25 centered reflections from

a crystal of the size 0.10)0.15)0.50 mm³in the range

108-Q-138 gave a triclinic unit cell of the dimen-

sions listed in Table 3. Data were collected from one

half of the reflection sphere in the range 28-Q-248

Ž .

y1046 6

Ž .

C 34

y1873 6

Ž .

C 35

y1631 6

y1942 5

6005 3

Ž .

74 1

Ž .

y1558 4

C 36

y532 5

6552 2

60 1

Ž .

C 41

1612 4

Ž .

y1171 3

7802 2

7676 2

41 1

54 1

Ž .

y1858 4

Ž .

C 42

2530 5

2193 6

928 6

Ž .

C 43

y3046 4

7976 3

Ž .

66 1

Ž .

Enraf–Nonius CAD diffractometer, Mo K_aradiation,

Ž .

y3586 4

C 44

8390 3

72 1

graphite monochromator, filter factor 15.41 . An empir-

ical absorption correction based on the intensities of 9

reflections was applied. The structure was solved by the

Patterson method in the space group P1 No. 2 using

the SHELXS86 28 program package. Hydrogen atoms

Ž .

C 45

14 5

Ž .

y2898 4

8540 3

8247 2

64 1

51 1

Ž .

y1710 4

Ž .

C 46

355 5

Ž .

C 50

5546 4

5120 5

2983 3

7364 2

Ž .

38 1

Ž .

C 51

3481 4

6698 2

48 1

Ž .

C 52

6150 5

Ž .

3527 4

6214 2

6521 2

62 1

59 1

Ž .

C 53

7247 5

6317 4

5322 5

3704 5

3600 4

5156 4

7314 4

3011 4

Ž .

C 54

1515 4

6598 2

Ž .

50 1

Ž .

C 55

749 4

5956 2

57 1

Ž .

Table 3

C 56

337 4

6199 2

6867 2

7192 2

7298 2

6003 3

5425 5

6044 6

5694 7

51 1

. Ž . .x

Crystallographic data for ReCl CO C₁₀H₁₀PPh₂)CDCl₃

Ž .

41 1

C 57

698 3

Ž .

39 1

2)CDCl₃

C 58

1476 3

Ž .

51 1

C 59

3513 4

Chemical formula

Formula weight

C₃₇H₃₀ClO₃P₂Re)CDCl₃

806.25q120.37

298

Ž .

2433 6

Ž .

80 1

C 61

5651 5

Ž .

111 2

Cl 2B

2065 10

Ž .

1424 10

2372 13

Ž .

1061 12

4308 7

Ž .

Temperature K

Ž .

132 3

Cl 3B

4348 8

6658 10

Ž .

6558 9

Ž .

P1 No. 2

space group

Ž .

121 2

Cl 4B

Ž .

a pm

945.1 5

Ž .

1113.9 6

Ž .

149 4

Cl 2A

4364 7

5457 5

6031 5

5779 9

b pm

Ž .

134 3

Cl 3A

4234 8

6894 9

Ž .

1888.5 10

c pm

Ž .

175 5

Cl 4A

6199 11

Ž .

a 8

92.36 3

Ž .

b 8

89.98 3

Ž .

113.49 2

is defined as one third of the trace of the orthogonalized U

i j

Ž .

tensor.

Ž .

V pm3

1.821 2 )10

l pm

70.930

1.690

4.60

0.0211

0.0502

r_calcg cm

were included in fixed positions, coupled to their re-

spective carbon atoms. Least squares cycles using the

m cm

Ž .x

R₁I)2s I

wR₂I)2s I

SHELXL93 29 program package led to the R values

given in Table 3. Atomic coordinates are listed in Table

4. Further details of the structure determination may be

Ž .x

Äw Ž

².²x w

².²x4^1r2

wR₂s Ýw F_cy F_or Ýw F_o.

(

)

T. Gutmann et al.rJournal of Organometallic Chemistry 552 1998 91–98

10 K. Raab, W. Beck, Chem. Ber. 118 1985 3830.

obtained from the Fachinformationszentrum Karlsruhe,

D-76344 Eggenstein-Leopoldshafen, on quoting the de-

pository number CSD407494, the names of the authors,

and the journal citation.

11 M. Appell, W. Sacher, W. Beck, J. Organomet. Chem. 333

1987 237.

12 W. Beck, K. Raab, Inorg. Synth. 28 1990 15.

13 D. Vitali, F. Calderazzo, Gazz. Chim. Ital. 102 1972 587.

14 D. Giusto, Inorg. Chim. Acta Rev. 6 1970 91.

15 J.F. Nixon, A. Pidcock, Ann. Rev. NMR Spectrosc. 2 1969

345.

Acknowledgements

16 R.D. Bertrand, F.B. Ogilvie, J. Verkade, J. Am. Chem. Soc. 92

1970 1908.

We are indebted to the Deutsche Forschungsgemein-

schaft and the Fonds der Chemischen Industrie for the

generous support of this work.

17 F.B. Ogilvie, J.M. Jenkins, J. Verkade, J. Am. Chem. Soc. 92

1970 1916.

18 Y. Koie, S. Shinoda, Y. Saito, Inorg. Nucl. Chem. Lett. 17

1981 147.

19 W.A. Schenk, W. Buchner, Inorg. Chim. Acta 70 1983 189.

20 X.C.R. Fontaine, J.D. Kennedy, B.L. Shaw, J.M. Vila, J. Chem.

References

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21 D. Baudry, A. Dormond, M. Visseaux, C. Monnot, H. Chardot,

w x

W.A. Schenk, T. Gutmann, J. Organomet. Chem., preceding

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Y. Lin, V.I. Bakhmutov, New J. Chem. 19 1995 921.

22 V.I. Bakhmutov, M. Visseaux, D. Baudry, A. Dormond, P.R.

w x

W.A. Schenk, C. Neuland-Labude, Z. Naturforsch. B 46 1991

573.

Richard, Inorg. Chem. 35 1996 7316.

23 N. Flitcroft, J.M. Leach, F.J. Hopton, J. Inorg. Nucl. Chem. 32

w x

W.A. Schenk, T. Gutmann, J. Organomet. Chem. 544 1997

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w x

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14 1975 1579.

1982 441.

w x

W. Tikkanen, Y. Fujita, J.L. Petersen, Organometallics 5 1986

25 W.D. Jones, J.A. Maguire, Organometallics 6 1987 1728.

26 D.G. Gusev, D. Nietlispach, A.B. Vymenits, V.L. Bakhmutov,

888.

w x

P.J. Harris, S.A.R. Knox, F.G.A. Stone, J. Organomet. Chem.

H. Berke, Inorg. Chem. 32 1993 3270.

148 1978 327.

27 S.P. Schmidt, W.C. Trogler, F. Basolo, Inorg. Synth. 28 1990

w x

F. Calderazzo, R. Poli, A. Barbati, P.F. Zanazzi, J. Chem. Soc.,

160.

Dalton Trans. 1984 1059.

28 G.M. Sheldrick, SHELXS 86, Program for Crystal Structure

Solution, Universitat Gottingen, Germany, 1986.

29 G.M. Sheldrick, SHELXL 93, Program for Crystal Structure

Refinement, Universitat Gottingen, Germany, 1993.

w x

W.K. Wong, F.L. Chow, H. Chen, T.C.W. Mak, J. Organomet.

Chem. 377 1989 C65.

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Ž .

W.K. Wong, F.W. Lee, Polyhedron 11 1992 863.

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