He gained the decisive break early in the second set when Ljubicic sent a backhand sailing wide.
Matteo Soragna gave Italy the lead when he made it 54-52 on a lay-up after a fast break early.
And Federer then took advantage of a poor Murray service game to break early in the third set and take charge of the match.
Martin, who won the Stella Artois title in 1994, consolidated his advantage with another break early in the second set and served out for victory.
After Granollers won the first set 6-3, Murray took a long injury break early in the second set, getting his left thigh and lower back massaged.
But Roddick showed admirable resolve to stay with his opponent in the fourth set, saving a break point early on with a huge serve out wide.
Teenage star Murray continued to show courage beyond his years as he and Rusedski regained the initiative after going a break down early in the third set.
"I had a few break points early on and I gave them up with average returning, so when I got a chance I knew I had to go for it, " she added.
Despite losing the set, the Poles continued to look the stronger pairing and Murray had to save a break point early in the third set before the world number three was broken in the sixth game.
That should have acted as a warning for Spain, but they were caught on the break again early in the second half and were lucky to escape when Almeida's cross span off Carlos Puyol and looped just beyond the far post.
But I got an early break in the fourth and that was important.
Serena Williams put an early break behind her to polish off the first set against Schiavone 6-3 in 34 minutes.
But the 21-year-old Serb broke once to take the first set and then recorded an early break in the second.
Once Broady and Farquharson had picked up their early break in the second set, Burton and Morgan were chasing the match.
The Warriors had to come from behind, having trailed 6-0 just before the break following an early penalty and a drop goal from Nick MacLeod.
Federer claimed the opening set after leading 3-0 at the beginning, and he achieved an early break in the opening game of the second set as well.
The Czech could not maintain that sort of form and conceded an early break in the deciding set, but still made Clijsters work hard for her win.
Williams secured an early break in the first game of the first set before Bartoli pegged her back but the number three seed closed out the opener 6-3.
An excellent early break from Rhodri Gomer-Davies nearly put Luke Charteris in at the corner, and Ceri Sweeney hit the post with a penalty resulting from the home side's pressure.
In the second set Mathieu raced to a 3-0 lead with an early break before cruising to victory to bring the scores level after a further 30 minutes of play.
Federer gained an early break in the opening set but his 22-year-old opponent hit back to tie it at 2-2 and then had chances to move ahead for the first time.
The current Netflix channel is tight enough that when you jump in you can have nice tight stops in case you called the break out too early and got it wrong.
He blew an early break to fall a break behind himself, and had to save three set points on his own serve in the ninth game in order to keep the set alive.
The Frenchman took advantage of a sluggish start by Novak to steal the first set but the Czech grabbed an early break in the second to get the match back on level terms.
An early break came after he traded a pound of beans a week for a year with a graphic designer in exchange for a folksy logo of a blue bottle for his fledgling company.
WSJ: Not the Same Old Grind: James Freeman of Blue Bottle | Creating
Her mood darkened further when Clijsters fashioned an early break in the decider, but at 3-4 the Belgian threw in a couple of double faults of her own before sending a drive volley long.
Soderling, who had lost all four of his previous matches against Djokovic, dropped only 11 points as he rattled through the second set and he had chances for an early break in the third.
In the second set, Clijsters gained an early break, saw off a break point in the fifth game to hold for a 4-1 lead, and she fought back from 0-40 down to serve out the match.
It was enough to secure the first set but not before a comeback from Del Potro, who carried the momentum into the second and grabbed an early break as he began to find his range more regularly.
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