(PECL mongo >= 1.5.0)
Examples:
Catching MongoDuplicateKeyException
<?php
$mc = new MongoClient("localhost");

$c = $mc->selectCollection("test", "test");

$c->insert(array('_id' => 1));
try {
    $c->insert(array('_id' => 1));
} catch (MongoWriteConcernException $e) {
    echo $e->getMessage(), "\n";
}
?>

The above examples will output something similar to:

localhost:27017: insertDocument :: caused by :: 11000 E11000 duplicate key error index: test.test.$_id_  dup key: { : 1 }