Synthesis and reactions of [Mo(2,6-lutidine)(phosphine)] derivatives

DOI: 10.1016/S0022-328X(97)00175-7

Source and publish data:

Journal of Organometallic Chemistry p. 63 - 70 (1998)

Update date:2022-07-29

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Authors:

Mehnert, Christian P.

Haggitt, Jane

Green, Malcolm L. H.

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Article abstract of DOI:10.1016/S0022-328X(97)00175-7

The syntheses of the η-lutidine(phosphine)molybdenum compounds [Mo(η⁶-NC₅H₃Me₂-2,6)L ₃] (L = PMe₃ 1, PPh₂ H 2, PPhMe₂ 3), [Mo(η⁶-NC₅H₃

Full text of DOI:10.1016/S0022-328X(97)00175-7

Journal of Organometallic Chemistry 550 1998 63–70

w ž

/ž

Synthesis and reactions of Mo 2,6-lutidine phosphine derivatives

)

Christian P. Mehnert , Jane Haggitt, Malcolm L.H. Green

Inorganic Chemistry Laboratory, South Parks Road, Oxford, OX1 3QR, UK

Received 18 December 1996

Abstract

x Ž

The syntheses of the h-lutidine phosphine molybdenum compounds Mo h -NC₅H₃Me₂-2,6 L₃LsPMe₃1, PPh₂H 2, PPhMe₂3 ,

.Ž

x .x

x Ž

Mo h -NC₅H₃Me₂-2,6 CH₃C CH₂PPh₂

HNC₅H₃Me₂-2,6 CH₃C CH₂PPh₂

4, Mo h -HNC₅H₃Me₂-2,6 L₃BF₄LsPMe₃5, PPh₂H 6, PPhMe₂7 , Mo h -

.Ž

x .x w ³x

BF₄8 and Mo h -H₃BNC₅H₃Me₂-2,6 L₃LsPPh₂H 9, PPhMe₂10 are described. The

crystal structures of complex 2 and 5 have been determined. q 1998 Elsevier Science S.A.

Keywords: Molybdenum; h-arene; Phosphine; Crystal structure; Metal vapour synthesis

1. Introduction

Over the last three decades the chemistry of bis h-

2. Results and discussion

.₂x

1 with the neat

Treatment of Mo h-2,6-lutidine

phosphine ligands PPh₂H and PPhMe₂at room temper-

.Ž ₃x

arene metal sandwich compounds has been well estab-

lished 1–3 . Although analogous sandwich complexes

which incorporate a heteroatom such as N, P or As into

ature gives the complexes Mo h-2,6-lutidine PPh₂H

.Ž

₃x

2 and Mo h-2,6-lutidine PPhMe

3, respectively.

w²

x²₃

₂x

the arene ring 4–6 have been prepared their chemistry

is virtually unexplored. Treatment of the well known

Warming a toluene solution of Mo h-2,6-lutidine

x₃

with the tridentate phosphine ligand CH C CH₂PPh

.₂x

bis-h-arene molybdenum compound Mo h-arene

with tertiary phosphines or phosphites gives the half

.Ž

³w

to 808C gives Mo h-2,6-lutidine CH₃C CH₂PPh₂

4. The complexes 2–4 were purified by column chro-

. x

sandwich compounds Mo h-arene PR , which ex-

matography on alumina at low temperature y208C .

The compounds 2–4 are bright red, moderately air

stable microcrystalline solids and very soluble in THF

and toluene, sparingly soluble in Et₂O and virtually

insoluble in pentane. The solids 2–4 melt in a sealed

capillary without decomposition at 1238C, 1398C, and

2758C, respectively.

hibit an extensive chemistry of the Mo h-arene moiety

1–3,9–15 . The complex Mo h-2,6-lutidine , first

prepared by Wucherer and Muetterties using metal

. x

w x

vapour synthesis techniques 7 has been fully charac-

w x

terised 8 but no reaction chemistry was reported.

Recently, we described the improved synthesis of

Mo h-2,6-lutidine using our bell-jar reactor 17 and

a modified work-up procedure, which enabled us to

produce the lutidine arene complex on a scale of 3–4 g

w x

Treatment of the neutral half-sandwich complexes

1–4 with one equivalent of HBF PEt₂O at y308C in a

Et₂O solution causes an immediate protonation and the

16 . We showed trimethylphosphine reacted with

complexes Mo h -HNC₅H₃Me₂-2,6 L₃BF

L s

Mo h-2,6-lutidine

to give the complex Mo h-2,6-

₃x ²w

⁴w

PMe₃5, PPh₂H 6, PhMe₂

.Ž

x₃

and Mo h -

.Ž

lutidine PMe

chemistry of Mo h-2,6-lutidine 1.

1 16 . Here we describe further the

w³

HNC₅H₃Me₂-2,6 CH₃C CH₂PPh₂

BF₄8 can be

isolated in almost quantitative yields. The complexes 6

and 7 melt without decomposition at 968C and 1538C,

respectively. The compound 8 decomposes at ca. 2508C.

The complexes 5–8 are soluble in THF and acetone, but

insoluble in Et₂O and pentane. Although the complexes

6–8 are stable in air after several hours but complex 5

decomposes immediately on exposure to air.

)

Corresponding author.

¹Dedicated to Professor Ken Wade on the occasion of his 65th

birthday.

²Current address: Department Of Chemical Engineering, Mas-

sachusetts Institute Of Technology, 66–553, Cambridge 02139, USA.

0022-328X

(

)

C.P. Mehnert et al.rJournal of Organometallic Chemistry 550 1998 63–70

Table 1

Analytical and spectroscopic data

Compound^a

Spectroscopic data^b1

1. Dark red

H : 1.19 27, m, PC H₃, 2.35 6, s, C₀C H₃, 3.68 2, m, H_m, 3.81 1, m, H_p

C, 44.1 44.55

H, 8.3 8.4

C : 23.9 2, s, C₀CH₃, 26.9 9, m, PCH₃, 68.0 2, s, C_m, 73.1 1, s, C_p, 103.1 2, s, C₀

N, 3.25 3.25

Mre 428 P^qEI

2. Bright red

P : 6.33 3, s, PCH₃

H : 2.10 6, s, C₀C H₃, 4.09 2, m, H_m, 5.10 1, m, H_p, 6.90 3, d Js322.7 PH , 6.97 18, m, P C₆H₅, 7.33

12, m, P C₆H₅

C, 47.8 47.5

H, 5.8 5.65

C : 22.7 2, s, C₀CH₃, 71.8 2, s, C_m, 76.6 1, s, C_p, 108.7 2, s, C₀, 127.9, 128.2, 133.3 s, P C₆H₅, 139.9

6, m, C_i

N, 4.6 4.6

Mre 763 P^qFAB

3. Bright red

P : 48.34 3, d Js324.2 PH

H : 1.42 18, s, PC H₃, 2.17 6, s, C₀C H₃, 3.76 2, m, H_m, 4.48 1, m, H_p, 7.15 9, m, P C₆H₅, 7.67

6, m, P C₆H₅

C, 60.4 60.3

H, 6.8 6.85

C : 23.2 2, s, C₀CH₃, 25.9 6, s, PCH₃, 69.4 2, s, C_m, 74.4 1, s, C_p, 105.0 2, s, C₀, 127.6, 128.2, 131.7

s, P C₆H₅, 145.7 3, m, C_i

N, 2.4 2.3

Mre 619 P^qFAB

4. Bright red

P : 16.51 3, s

H : 1.13 3, s, C H₃C , 2.17 6, s, CC H₂, 2.35 6, s, C₀C H₃, 4.02 2, m, H_m, 5.02 1, m, H_p, 6.89

.x .x

18, m, P C₆H₅, 7.26 12, m, P C₆H₅

C, 69.5 69.65

H, 6.0 5.8

C : 24.5 2, s, C₀CH₃, 38.8 1, s, CH₃C , 40.2 3, s, CCH₂, 74.7 2, s, C_m, 78.3 1, s, C_p, 110.8 2, s, C₀, 127.4,

. x

132.5 m, P C₆H₅, 144.6 6, m, C_i

N, 1.8 1.7

Mre 829 P^qFAB

5. Red

P : 42.41 3, s

H : 1.42 27, m, PC H₃, 2.40 6, s, C₀C H₃, 3.81 2, m, H_m, 4.39 1, m, H_m

C, 36.9 37.0

H, 7.1 7.2

C : 18.9 2, s, C₀CH₃, 24.7 9, m, PCH₃, 64.6 2, s, C_m, 73.1 1, s, C_p, 92.3 2, s, C₀

N, 2.65 2.7

x^q

Mre 428 P-BF₄

P : 0.48 3, s

FAB

IR: 3246vs^e

6. Red

H : 1.98 6, s, C₀C H₃, 4.49 2, m, H_m, 5.81 1, m, H_p, 6.73 3, d Js316.6 PH , 7.24 18, m, P C₆H₅, 7.31

12, m, P C₆H₅

C, 60.8 60.8

H, 5.2 5.1

C : 23.0 2, s, C₀CH₃, 72.7 2, s, C_m, 77.4 1, s, C_p, 102.0 2, s, C₀, 134.0, 134.9, 138.3 s, P C₆H₅, 140.6

6, m, C_i

N, 1.6 1.65

Mre 763 P-BF₄

P : 29.20 3, s

FAB

IR: 3194vs^e

7. Red

H : 1.63 18, s, PC H₃, 2.08 6, s, C₀C H₃, 4.11 2, m, H_m, 5.29 1, m, H_p, 7.44 9, m, P C₆H₅, 7.65

6, m, P C₆H₅

C, 52.8 52.8

H, 6.3 6.1

C : 18.4 2, s, C₀CH₃, 24.0 6, s, PCH₃, 66.2 2, s, C_m, 73.4 1, s, C_p, 93.3 2, s, C₀, 129.2, 130.2, 132.0

s, P C₆H₅, 142.4 3, m, C_i

N, 2.2 2.0

Mre 619 P-BF₄

P : 8.34 3, s

FAB

IR: 3219vs^e

8. Pink

H : 1.64 3, s, C H₃C , 2.30 6, s, C₀C H₃, 2.45 6, s, CC H₂, 4.34 2, m, H_m, 5.38 1, m, H_p, 7.11

.x .x

18, m, P C₆H₅, 7.21 12, m, P C₆H₅

C, 62.5 63.0

H, 5.6 5.4

C : 15.6 1, s, CH₃C , 19.7 2, s, C₀CH₃, 38.7 3, s, CCH₂, 70.5 2, s, C_m, 74.5 1, s, C_p, 128.7, 132.9

m, P C₆H₅

N, 1.4 1.5

Mre 829 P-BF₄

P : 32.79 3, s

FAB

IR: 3208vs^e

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C.P. Mehnert et al.rJournal of Organometallic Chemistry 550 1998 63–70

Table 1 continued

Compound^a

Spectroscopic data^b

9. Orange

H : 1.97 6, s, C₀C H₃, 3.99 2, m, H_m, 5.39 1, m, H_p, 6.57 3, d Js333.3 PH , 7.11 30, m, P C₆H₅

C, 66.7 66.6

H, 5.7 5.85

C : 22.9 2, s, C₀CH₃, 71.0 2, s, C_m, 72.3 1, s, C_p, 106.1 2, s, C₀, 128.1, 128.8, 132.9 s, P C₆H₅, 140.9

6, s, C_i

N, 1.9 1.8

P : 43.72 3, d Js333.3 PH

B : y14.0 1, s

10. Orange

H : 1.51 18, s, PC H₃, 2.47 6, s, C₀C H₃, 3.68 2, m, H_m, 4.70 1, m, H_p, 7.34 9, m, P C₆H₅, 7.54

6, m, P C₆H₅

C, 57.8 59.0

H, 7.1 7.2

C : 22.1 2, s, C₀CH₃, 24.1 6, s, PCH₃, 68.6 2, s, C_m, 72.4 1, s, C_p, 103.8 2, s, C₀, 127.9, 129.0, 131.2

s, P C₆H₅, 143.2 3, m, C_i

N, 2.2 2.2

x^q

Mre 619 P-BH₃

P : 11.45 3, s

FAB

B : y18.6 1, s

Analytical data given as: found calculated %.

^b1H at 300.13 MHz, ¹³C at 75.5 MHz and P at 121.6 MHz. NMR data given as: chemical shift d , relative intensity, multiplicity sssinglet,

dsdoublet, tstriplet, msmultiplet , coupling constant in Hz and assignment. The labelling of atoms is given in the structure of 2 in the

Scheme 1. Infrared data in Nujol mulls cm . The Mre values refer to the ⁹⁸Mo isotope.

In ²H₆benzene.

In ²H₆acetone.

Assigned to n NH frequency.

In ²H₂dichloromethane.

Ž .

LsPPhMe₂, neat PPhMe₂at room temperature for 18 h, yield 59%. iii Triphos in toluene at 808C for 15 h, yield 55%. iv Addition of

Ž .

Scheme 1. i Neat PMe₃at room temperature for 12 h, yield 79%. ii For LsPPh₂H, neat PPh₂H at room temperature for 24 h, yield 78%. For

Ž .

HBF₄PEt₂O to Et₂O solution at y788C, yield 75%. v For LsPPh₂H, addition of HBF₄PEt₂O to Et₂O solution at y308C, yield 96%. For

LsPPhMe₂, addition of HBF₄PEt₂O to Et₂O solution at y308C, yield 94%. vi For LsPPh₂H, addition of BH₃PTHF to Et₂O solution at

y108C, yield 80%. For LsPPhMe₂, addition of BH₃PTHF to Et₂O solution at room temperature, yield 92%. vii Addition of HBF₄PEt₂O to

Et₂O solution at y308C, yield 96%.

(

)

C.P. Mehnert et al.rJournal of Organometallic Chemistry 550 1998 63–70

Fig. 2. Perspective view of molecule 5.

Fig. 1. Perspective view of molecule 2.

Treatment of a diethyl ether solution of complexes 2

and 3 with one equivalent of the Lewis acid, complex

BH₃PTHF at low temperature results in the formation

were made and their structures have been determined.

The perspective views of the two molecules are shown

in Figs. 1 and 2, respectively. Selected bond angles and

distances are listed in Tables 2 and 3, and the fractional

atomic coordinated are given in Tables 4 and 5. The

distances between the coordinated lutidine and the

of orange solids, which have been identified as the

Lewis-acid–base adducts Mo h -H₃BNC₅H₃Me₂-

2,6 L₃LsPPh₂H 9, PPhMe₂10 in almost quantita-

tive yield. They are soluble in benzene and CH₂Cl₂, but

insoluble in Et₂O and pentane. In solution, an equilib-

rium between the starting materials and the products, 9

and 10, is observed by proton NMR. The addition of an

excess of BH₃PTHF to solutions of 9 and 10 in deuter-

ated benzene shifts the equilibrium towards product

formation. Reactions between other Lewis acids like

Ž .

molybdenum centre range from 2.267 3 to 2.310 3 A.

Ž . Ž .

In the compound 2 the carbon atoms C 1 , C 3 and

Ž .

C 5 are slightly drawn out of the ring plane and

towards the metal atom and give the lutidine a chair-like

conformation. The methyl groups of the ring in ortho

positions are slightly bent out of the plane and away

from the molybdenum. The intra-ring distances of

Ž . Ž .

BF₃and B C₆F₅and 6 or 7 resulted in the decomposi-

N 1 –C 1 and N 1 –C 5 in the coordinated lutidine

Ž .

tion of 1.

range from 1.386 4 and 1.396 4 A, respectively. These

bond distances are shorter than the remaining carbon–

carbon bond lengths in the ring which are found be-

tween 1.412 5 and 1.419 5 A. Similar observations

have been made for other related complexes 8 .

The analytical and spectroscopic data characterising

the compounds 1–10 are given in Table 1. A summary

of the reactions and the conditions is shown in Scheme

Ž .

w x

Crystals of 2 and 5 suitable for X-ray diffraction

Table 3

Ž .

Table 2

Selected interatomic distances A and angles 8 for 5

Ž .

Selected interatomic distances A and angles 8 for 2

Ž .

–P 1

–P 2

Ž .

2.451 7

2.466 7

Ž .

P 1

Ž .

–P 2

–P 3

Ž .

92.44 2

–Mo

Ž .

–P 3

Ž .

93.43 3

Ž .

88.32 2

Mo –P 1

2.421 8 P 1

–Mo

–P 2

Ž .

91.10 3

Ž .

89.66 2

Mo –P 2

Ž .

Mo –P 3

Mo –N

2.413 9 P 1

–P 3

2.458 7

P 2

–P 3

Ž . Ž .

Ž .

85.60 3

Ž .

2.395 8 P 2

–P 3

–N

Ž .

2.245 2

P 1

–N 1

156.77 6

Ž . Ž .

Ž .

94.99 7

Ž .

2.298 2 P 1

Ž . Ž .

–N 1

–C 1

2.259 3

P 2

–N 1

98.35 6

Ž .

–N 1

Ž .

102.46 7

Ž .

P 3

Ž .

Mo –C 1 2.269 3 P 2

Ž . Ž . Ž .

–C 2

2.304 3

–N 1

112.13 6

Ž .

–N 1

Ž .

Mo –C 2 2.310 3 P 3

169.56 7

–C 3

2.269 3

–P 1

–C 11

125.2 1

Ž . Ž .

Ž .

Mo –C 3 2.267 3 Mo

–P 1

–C 111 126.5 1

–C 4

Ž .

2.300 3

–P 1

–C 12

115.7 1

Ž . Ž .

Ž .

Mo –C 4 2.310 3 Mo

Ž . Ž .

–P 1

–C 121 119.1 1

–C 5

2.238 3

–P 1

–C 13

113.1 1

Ž .

Mo –C 5 2.280 3 C 111 –P 111 –C 121 99.2 1

–CEN 1.777

C 11

–P 1

–C 12

100.3 1

Ž .

Mo –CEN 1.805

C 1

–N 1

–C 5

116.6 3

–C 1

1.411 4

C 1

–N 1

–C 5

123.2 2

Ž .

119.0 3

Ž .

–C 1 1.386 4 C 1

–C 2

–C 3

–C 5

1.405 3

C 1

–C 2

–C 3

120.6 3

Ž .

118.6 3

Ž .

–C 5 1.396 4 C 3

–C 4

Ž .

–C 5

C 1

–C 2

1.406 4

C 3

–C 4

–C 5

119.9 2

Ž . Ž . Ž .

Ž .

–C 4

Ž .

123.1 3

Ž .

C 1 –C 2 1.417 4 N 1

–C 5

C 2

–C 3

1.415 4

N 1

–C 5

–C 4

117.8 2

Ž . Ž . Ž .

Ž .

C 2 –C 3 1.412 5 CEN

–Mo

–P 1

121.3

123.47

131.03

C 3

–C 4

Ž .

1.414 4

CEN

–Mo

–P 1

120.80

127.94

126.54

Ž . Ž . Ž .

Ž .

C 3 –C 4 1.419 5 CEN

Ž . Ž . Ž .

–P 2

C 4

–C 5

1.419 4

–P 2

Ž .

–P 3

Ž .

C 4 –C 5 1.418 5 CEN

–P 3

Ž . Ž .

CEN denotes the centroid of the NC 1 –C 5 ring.

(

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C.P. Mehnert et al.rJournal of Organometallic Chemistry 550 1998 63–70

Table 5

The molybdenum atom in 5 is not equidistant to all

Fractional atomic coyordinates for compound 5

Atom

Ž .

the lutidine ring atoms and the atoms C 3 and N 1 are

slightly bent out of the ring plane towards the molybde-

num atom. The protonation of the nitrogen atom results

Ž .

0.33138 1

Mo 1

0.71036 2

0.53267 6

0.86852 7

0.72529 7

0.7844 3

0.6521 3

0.5675 3

0.6146 3

0.7478 3

0.5440 3

0.3940 3

0.4593 3

0.8897 3

0.8484 3

1.0356 3

0.6870 3

0.8814 3

0.6238 3

0.8791 3

0.8111 3

0.8286 2

0.7933 3

0.9156 2

0.7693 2

0.23825 2

0.28971 5

Ž .

0.41491 4

P 1

Ž . Ž .

in a slight lengthening of the N 1 –C 1 and N 1 –C 5

Ž .

0.31789 5

Ž .

0.42110 4

P 2

bonds N–C _avgs1.391 A for 2; N–C _avgs1.408 A

Ž .

0.08011 5

Ž .

0.40884 4

P 3

Ž .

for 5 .

In conclusion, the new reactions and compounds are

shown in the Scheme. Generally it is found that the

Ž .

0.3330 2

Ž .

0.2303 2

C 1

Ž .

0.3485 2

Ž .

0.2311 2

C 2

Ž .

0.2647 2

Ž .

0.2315 2

C 3

Ž .

0.1646 2

Ž .

0.2223 2

C 4

Ž .

C 11

chemistry is similar to that of Mo h-toluene , how-

Ž .

0.1470 2

Ž .

0.2222 2

C 5

Ž .

0.3162 3

Ž .

0.5220 2

Ž .

0.2059 2

Ž .

0.4123 2

C 12

Table 4

Ž .

0.4102 2

Ž .

0.3836 2

C 13

Fractional atomic co-ordinates for compound 2

Ž .

0.2840 2

Ž .

0.5257 2

C 21

Ž .

0.4552 3

Ž .

0.4298 2

C 22

Atom

Ž .

0.3060 3

Ž .

0.3929 2

C 23

Ž .

0.36841 8

Ž .

0.33924 8

Ž .

0.29935 1

Mo 1

Ž .

0.13077 3

0.35912 3

Ž .

0.0704 2

Ž .

0.5146 2

C 31

Ž .

0.33923 4

P 1

P 2

P 3

Ž .

0.0179 2

Ž .

0.4114 2

C 32

Ž .

0.30751 4

0.02706 8

0.12859 8

Ž .

0.3729 2

C 33

y0.0243 2

0.4157 2

0.0485 2

Ž .

0.17178 4

0.10501 8

0.27056 8

Ž .

0.2161 2

C 101

Ž .

0.4131 1

N 1

Ž .

0.1436 3

0.4765 3

Ž .

0.2017 2

C 501

Ž .

0.3728 2

C 1

0.0033 3

0.4180 3

Ž .

0.2322 2

Ž .

0.2217 1

N 1

Ž .

0.3005 2

C 2

y0.0588 3

Ž .

0.0270 4

0.4420 3

Ž .

y0.2909 3

Ž .

0.3156 2

B 1

Ž .

0.2652 2

C 3

0.5225 3

Ž .

0.2987 1

F 1

Ž .

y0.3277 1

Ž .

0.3064 2

C 4

Ž .

C 11

0.1690 4

0.5897 3

Ž .

y0.2037 2

Ž .

0.2717 1

F 2

Ž .

0.3790 2

C 5

0.2239 3

0.5627 3

Ž .

0.3960 1

F 3

0.7866 2

0.7062 2

y0.2704 2

Ž .

y0.0840 4

0.3396 4

0.4148 2

Ž .

0.4282 2

Ž .

y0.3662 2

Ž .

0.2948 1

F 4

Ž .

C 51

0.3694 4

0.6391 3

Ž .

C 111

C 112

C 113

C 114

C 115

C 116

C 121

C 122

C 123

C 124

C 125

C 126

C 211

C 212

C 213

C 214

C 215

C 216

C 221

C 222

C 223

C 224

C 225

C 226

C 311

C 312

C 313

C 314

C 315

C 316

C 321

C 322

0.4269 3

Ž .

0.1897 3

0.3142 2

Ž .

0.2486 2

Ž .

0.4647 4

0.1710 4

Ž .

0.4996 5

0.0548 4

0.2274 2

Ž .

0.4955 4

y0.0458 4

0.2705 2

ever, the h-lutidine ligands of 1 are more readily dis-

placed.

Ž .

0.4592 4

Ž .

y0.0276 4

0.3356 2

Ž .

0.3584 2

Ž .

0.4263 3

0.0903 4

Ž .

0.5129 3

0.4724 3

Ž .

0.3280 2

Ž .

0.3800 2

Ž .

0.6470 3

0.5096 3

Ž .

0.7556 3

Ž .

0.6067 4

0.3691 2

Ž .

0.3048 2

3. Experimental

Ž .

0.7317 4

0.6637 4

Ž .

0.5992 4

0.6278 4

0.2534 2

Ž .

0.2656 2

All preparations and manipulations were carried out

under an inert atmosphere of dinitrogen using either

standard Schlenk techniques or a dry box, unless other-

wise stated. All solvents were thoroughly deoxygenated

before use either by repeated evacuation followed by

admission of dinitrogen, or by bubbling dinitrogen

through the solvent for approximately 15 min. Solvents

Ž .

0.4889 3

0.5334 3

Ž .

y0.0175 3

y0.0161 3

0.2313 2

Ž .

y0.1572 4

y0.0767 4

0.1874 2

Ž .

y0.1890 4

y0.1842 4

0.1286 2

Ž .

y0.0840 4

Ž .

y0.2328 4

Ž .

0.1126 2

Ž .

0.1557 2

0.0546 4

y0.1739 4

Ž .

y0.0652 3

Ž .

0.2133 2

0.0884 4

Ž .

0.0587 3

Ž .

0.3897 2

0.1056 3

Ž .

y0.0791 3

Ž .

0.3868 2

0.0895 3

were pre-dried over activated 4A molecular sieves and

Ž .

0.4508 2

0.1480 4

y0.1279 3

then distilled over sodium toluene , sodiumrpotassium

Ž .

y0.0387 4

Ž .

0.5175 2

0.2227 4

alloy and benzophenone benzene , sodium and benzo-

Ž .

0.5206 2

0.2404 4

0.0991 4

phenone diethyl ether, THF , or calcium hydride pen-

Ž .

0.1823 3

0.1481 3

0.4573 2

Ž .

tane, 40r60 petroleum ether, heptane, dichloromethane

under slow continuous stream of dinitrogen.

Perdeuterated solvents for NMR spectroscopy were de-

oxygenated and then dried over calcium hydride di-

chloromethane or potassium benzene and toluene .

y0.0722 3

0.1985 3

0.1027 2

Ž .

0.1910 4

Ž .

0.2196 4

0.1185 2

Ž .

y0.3213 4

Ž .

0.0665 2

0.1689 4

Ž .

y0.0036 2

y0.3372 4

0.0950 4

Ž .

y0.0197 2

y0.2199 4

0.0711 4

Ž .

y0.0876 4

Ž .

0.0329 2

0.1241 3

Ž .

0.1132 2

Activated, neutral, Brockmann I, standard grade, ;150

0.1856 3

0.3759 3

Ž .

0.1409 4

0.4875 3

0.0935 2

Ž .

0.0530 2

mesh alumina Al₂O₃was used for chromatography

and deoxygenated before use by repeated evacuation

followed by admission of dinitrogen. Celite 545 filtra-

tion aid Koch–Light was pre-dried at 1408C and

similarly deoxygenated before use. NMR spectra were

Ž .

C 323

C 324

C 325

C 326

0.2068 4

0.5716 4

Ž .

0.0327 2

0.3196 4

0.5456 4

Ž .

0.0512 2

0.3648 4

0.4349 4

Ž .

0.2968 4

Ž .

0.3494 4

Ž .

0.0901 2

(

)

C.P. Mehnert et al.rJournal of Organometallic Chemistry 550 1998 63–70

recorded on a Bruker AM ¹H, ¹³C and ³¹P NMR

spectra were recorded at 300.13, 75.5, and 121.6 MHz,

under reduced pressure to leave a red oily residue.

Extraction into THF and precipitation with an excess of

pentane yielded a bright red, microcrystalline solid.

respectively . The spectra were referenced internally

Ž¹Ž¹³

using the residual protio solvent H and solvent

Yield, 510 mg 59% .

resonances and measured relative to TMS ¹H and ¹³C;

ds0 ppm , or referenced externally to BF₃PEt₂O ¹¹B;

[

(

3 .4 . S yn th esis o f

M o h -N C ₅H ₃M e ₂-

Ž¹⁹

F; ds0 ppm or 85% H₃PO₄

)(

[

(

) ] )] ( )

ds0 ppm , CFCl₃

2,6 CH₃C CH₂P C₆H₅

Ž³¹

P; ds0 ppm . All chemical shifts are quoted in d

₂x

ppm and coupling constants are given in Hertz. Elec-

tron Impact mass spectra were recorded on an AEI MS

302 mass spectrometer, updated by a data-handling

system supplied by Mass Spectrometry Services Ltd.

Fast Atom Bombardment mass spectra were obtained by

the EPSRC Mass Spectrometry Service Centre. Infrared

spectra were recorded on a Perkin-Elmer 1710 FTIR

A mixture of Mo h -NC₅H₃Me₂-2,6

0.4 g, 1.29

mmol and triphos 1 g, 1.6 mmol in 10 mL toluene

was heated at 808C for 15 h. The dark red solution was

evaporated to dryness and the resulting oily residue was

purified by column chromatography on alumina at

y258C. Unreacted triphos was removed with light

petroleum 40–608C rEt₂O 1r1 . Further elution with

spectrometer in the range 400 cm^y1to 4000 cm^y1

Samples were either prepared as Nujol mulls between

KBr plates, as KBr discs or as dilute solutions in a

solution cell with KBr windows: all data given are in

wavenumbers cm . Elemental analyses were per-

formed by the Oxford Analytical Laboratory.

Et₂OrTHF 9r1 afforded a red band, from which

complex 4 was isolated as a red oil after evaporation of

the solvent in vacuo. The resulting oily residue was

triturated with pentane to give an intense bright red,

microcrystalline solid. Yield, 590 mg 55% .

[

(

3.5. Synthesis of

)( ) ][ ] ( )

M o h -H N C ₅H ₃M e ₂-

[

(

)(

) ] ( )

3.1. Synthesis of Mo h -NC₅H₃Me₂-2,6 PMe₃

2,6 PMe₃BF₄

₂x

The complex Mo h -NC₅H₃Me₂-2,6

210 mg,

To a deep red solution of Mo h -NC₅H₃Me₂-

.Ž

₃x

0.68 mmol was stirred for 12 h in 3 mL neat PMe₃at

room temperature. The resulting red–brown solution

was evaporated to dryness, extracted into pentane and

crystallised at y808C to give dark red crystals. Yield,

2,6 PMe₃

200 mg, 0.46 mmol in 50 mL Et₂O a

. Ž

solution of HBF₄PEt₂O 85% 0.07 mL, 0.46 mmol

was added at y788C to give a beige precipitate. After

the mixture was warmed to room temperature, the

colourless supernatant was decanted off and the result-

ing residue was dried in vacuo. The solid was washed

with Et₂O and crystallisation at y808C from a concen-

trated solution of THF yielded dark red crystals. Yield:

230 mg 79% .

[

(

)(

) ] ( )

3.2. Synthesis of Mo h -NC₅H₃Me₂-2,6 PPh₂H ₃

₂x

The complex Mo h -NC₅H₃Me₂-2,6

830 mg,

180 mg 75% .

2.68 mmol was dissolved in 5 mL neat PPh₂H and

stirred for 24 h at room temperature. The resulting red

mixture was brought onto alumina and a column chro-

matography at y258C was carried out to separated

unreacted PPh₂H ligand from 2. The free ligand was

[

(

M o h -H N C ₅H ₃M e ₂-

3.6. Synthesis of

)(

) ][

] ( )

2,6 PPh₂H ₃BF₄

.Ž

₃x

The complex Mo h -NC₅H₃Me₂-2,6 PPh₂H

eluted with light petroleum b.p. 40r60 . Further elu-

mg, 0.09 mmol in 25 mL Et₂O was treated with

. Ž

tion with a mixture of light petroleum 40–608C rEt₂O

HBF₄PEt₂O 85% 0.015 mL, 0.09 mmol at y308C

to give an orange precipitate. The mixture was warmed

to room temperature, the supernatant decanted off and

the resulting residue was dried in vacuo to give a red,

1r1 afforded a red fraction, from which complex 2

was obtained as a bright red, microcrystalline solid after

removal of the solvent in vacuo. Yield, 1.6 g 78% .

microcrystalline solid. Yield, 74 mg 96% .

[

(

)(

)₃]

3.3. Synthesis of Mo h -NC₅H₃Me₂-2,6 PPhMe₂

( )

[

(

3.7. Synthesis of

)( ) ][ ] ( )

M o h -H N C ₅H ₃M e ₂-

2,6 PPhMe₂BF₄

₂x

A solution of Mo h -NC₅H₃Me₂-2,6

430 mg,

1.39 mmol in 5 mL neat PPhMe₂was stirred for 18 h

at room temperature. The resulting red mixture was

brought onto alumina and separated by column chro-

matography at y258C. Excess PPhMe₂was removed

solution of complex Mo h -NC₅H ₃Me₂-

.Ž

₃x

2,6 PPhMe₂

240 mg, 0.39 mmol in 50 mL Et₂O

was cooled to y308C and treated with HBF₄PEt₂O

. Ž

85% 0.06 mL, 0.39 mmol to give a beige precipitate.

with a mixture of light petroleum 40–608C rEt₂O

The suspension was warmed to room temperature, the

supernatant decanted off and the residue dried under

reduced pressure. The resulting solid was extracted into

5r1 and further elution with Et₂OrTHF 9r1 gave a

red fraction from which the volatiles were removed

(

)

C.P. Mehnert et al.rJournal of Organometallic Chemistry 550 1998 63–70

THF and pentane was added until the precipitation of 7

was completed. The pale red supernatant was filtered

off and the remaining orange, microcrystalline solid was

structure was solved by the Patterson method. Hydro-

gens were included in the calculation but were not

refined. The final Rs3.95, R_ws4,54% for 445 least-

square parameters.

dried in vacuo. Yield, 260 mg 94% .

Crystal data for 5: C₁₆H₃₇BF₄MoNP₃, Ms519.1,

[

(

Ž .

3.8. Synthesis of

)(

M o h -H N C ₅H ₃M e ₂-

monoclinic, a s 10.513 5 , b s 13.133 5 , c s

[

(

) ] )][ ] ( )

Ž .

2,6 CH₃C CH₂P C₆H₅

BF₄8

16.879 3 A, bs90.78 4 , Us2330.2 A , space group

P2₁rc, Zs4, Mo-K a ls0.71069 A , D_cs1.48 g

cm^y3, ms7.84, F 000 s1072, Ts120 K. Crystal

dimensions 0.20=0.20=0.33 mm³. Of the 10091 re-

flections measured, total unique data 3625, 3015 were

.Ž

Com plex

M o h -NC ₅H ₃M e₂-2,6 CH ₃C-

₂x₃

70 mg, 0.08 mmol was dissolved

CH₂P C₆H₅

in 50 mL Et₂O and treated with HBF₄PEt₂O 85%

Ž .

0.012 mL, 0.08 mmol at y308C to give a pink

unique with I)3s I . The structure was solved by the

precipitate. The reaction mixture was warmed to room

temperature, the colourless supernatant was filtered off

and the residue dried under reduced pressure. The re-

sulting filtrate was washed with pentane and dried in

vacuo to yield an intense pink, microcrystalline solid.

Patterson method, to final Rs3.09, R_ws3.56% for

Ž .

239 least-square parameters. The H 1 hydrogen was

refined in the least squares analysis and the remaining

hydrogens were placed geometrically. Corrections for

Lorentz and polarization effects as well as empirical

Yield, 70 mg 96% .

correction for absorption 18 were applied. Crystallo-

graphic calculations were carried out using the CRYS-

[

(

3.9. Synthesis of

M o h -H₃BNC₅H₃M e₂-

TALS program package 19 on Micro VAX 3800

computer. Neutral atom scattering factors were taken

)(

) ] ( )

2,6 PPh₂H ₃

from the usual sources 20 . Hydrogen atom coordi-

nates, thermal parameters, and complete lists of remain-

ing bond lengths and angles have been deposited at the

Cambridge Crystallographic Data Centre.

.Ž

red solution of Mo h -NC₅H ₃Me₂-

₃x

2,6 PPh₂H 200 mg, 0.26 mmol in 50 mL Et₂O a

THF solution of BH₃PTHF 1M, 0.26 mL, 0.26 mmol

was added at y108C. The mixture was warmed to room

temperature and light petroleum 40–608C was added

until the precipitation of 9 was completed. The super-

natant was decanted off and the resulting orange, micro-

crystalline solid was dried under reduced pressure. Yield,

Acknowledgements

Dedicated to Professor Ken Wade FRS on the occa-

sion of his 65th birthday in recognition of his outstand-

ing contributions to organometallic and inorganic chem-

istry. The data collection for the determination of single

crystal X-ray diffraction was carried out by Prof. M.B.

Hursthouse and S. Coles at the EPSRC crystallography

facility in Cardiff.

160 mg 80% .

[

(

Mo h -H₃BNC₅H₃Me₂-

3.10. Synthesis of

)(

2,6 PPhMe₂

) ] ( )

.Ž

₃x

The complex Mo h -NC₅H₃Me₂-2,6 PPhMe₂

150 mg, 0.24 mmol in 50 mL Et₂O was treated with a

THF solution of BH₃PTHF 1M, 0.5 mL, 0.5 mmol at

room temperature to give an orange precipitate. After 2

References

h of additional stirring light petroleum 40–608C was

added until the precipitation of 10 was completed. The

supernatant was filtered off and the resulting orange,

microcrystalline solid dried in vacuo. Yield, 140 mg

w x

Ž .

M.L.H. Green, J. Organomet. Chem. 200 1980 119.

M.L.H. Green, J. Knight, J. Chem. Soc., Dalton Trans. 1976

213.

w x

Ž .

W.E. Silverthorn, Adv. Organomet. Chem. 13 1975 47.

C. Elschenbroich, J. Kroker, W. Massa, M. Wunsch, A.J. Ashe

III, Angew. Chem., Int. Ed. Engl. 25 1986 571.

w x

92% .

w x

3.11. Crystal structure determination of complex 2 and

C. Elschenbroich, J. Koch, J. Kroker, M. Wunsch, W. Massa,

G. Baum, G. Stork, Chem. Ber. 121 1988 1983.

w x

C. Elschenbroich, M. Nowotny, B. Metz, W. Massa, J. Graulich,

K. Biehler, W. Sauer, Angew. Chem., Int. Ed. Engl. 30 1991

Crystal data for 2: C₄₃H₄₂MoNP₃, Ms761.67, tri-

547.

Ž .

clinic, as10.270 2 , bs10.364 3 , cs18.823 1 A,

w x

Ž .

w x

E.J. Wucherer, E.L. Muetterties, Organometallics 6 1987 1691.

E.J. Wucherer, E.L. Muetterties, Organometallics 6 1987 1696.

M.L.H. Green, J. Knight, J. Chem. Soc., Dalton Trans. 1974

311.

Ž .

a s 96.32 2 , b s 105.34 1 , g s 103.72 1 8, U s

w x

1844.9 A , space group P1, Zs2, Mo-K a ls

0.71069 A , D_cs1.37 g cm , ms5.05, F 000 s

788, Ts120 K. Crystal dimensions 0.15=0.20=0.30

mm³. Of the 8052 reflections measured, total unique

10 M.L.H. Green, L.C. Mitchard, W.E. Silverthorn, J. Chem. Soc.,

Dalton Trans. 1973 1403.

11 M.L.H. Green, L.C. Mitchard, W.E. Silverthorn, J. Chem. Soc.,

Ž .

data 5085, 4406 were unique with I)3s I . The

Dalton Trans. 1973 2177.

(

)

C.P. Mehnert et al.rJournal of Organometallic Chemistry 550 1998 63–70

12 M.L.H. Green, L.C. Mitchard, W.E. Silverthorn, J. Chem. Soc.,

17 C.P. Mehnert, A.N. Chernega, M.L.H. Green, J. Organomet.

Ž .

Chem. 513 1996 247.

Dalton Trans. 1973 1952.

13 M.L.H. Green, W.E. Silverthorn, J. Chem. Soc., Dalton Trans.

18 D.J. Walker, D. Stuart, Acta Crystallogr. Sec. A 39 1983 158.

19 D.J. Watkin, J.R. Carruthers, P.W. Betteridge, CRYSTALS

1973 301.

14 M.L.H. Green, J. Knight, L.C. Mitchard, G.G. Roberts, W.E.

User Guide, Chemical Crystallography, University of Oxford,

1985.

Silverthorn, J. Chem. Soc., Chem. Commun. 1972 987.

15 M.L.H. Green, L.C. Mitchard, W.E. Silverthorn, J. Chem. Soc.

20 Int. Tables for Crystallography, Vol IV, Kynoch, Birmingham,

A 1971 2929; M.L.H. Green, W.E. Silverthorn, J. Chem. Soc.,

1974, p. 99.

Chem. Commun. 1971 557.

16 W.D. McGhee, A. Sella, D. O’Hare, F.G.N. Cloke, C.P. Mehn-

ert, M.L.H. Green, J. Organomet. Chem. 459 1993 125.

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